CN102730759A - A preparing method for an ultra-pure ammonium tungstate - Google Patents

A preparing method for an ultra-pure ammonium tungstate Download PDF

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CN102730759A
CN102730759A CN2011100882003A CN201110088200A CN102730759A CN 102730759 A CN102730759 A CN 102730759A CN 2011100882003 A CN2011100882003 A CN 2011100882003A CN 201110088200 A CN201110088200 A CN 201110088200A CN 102730759 A CN102730759 A CN 102730759A
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ammonium tungstate
ammonium
tungstate
ammonia
acid
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范传景
范传业
邢奇生
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Abstract

The invention provides a preparing method for an ultra-pure ammonium tungstate, and the method comprises steps of adopting tungsten oxide, ammonium metatungstate, ammonium paratungstate, and ammonium tungstate as raw materials, adding pure water and liquefied ammonia (ammoniacal water) for dissolving the ammonia and mixing the solution uniformly under normal temperature, adding super acid for acid precipitation and crystallization under normal pressure after the extraction and purification of the solution, carrying out solid-liquid separation process after the acid precipitation is finished, and the ultra-pure ammonium tungstate is obtained after drying the separated ammonium tungstate. When the ammonia solution blending is carried out, the tungstate acid radical ion concentration in the main solution is controlled at 50-250 g/L and the solution PH is kept at 7.5-11.0; whereas the acid precipitation is carried out, end-point PH of the acid precipitation is controlled at 4.0-7.0. The purity of the ammonium tungstate products is greatly improved by adopting the method of the invention. The purity exceeds zero-level category of the ammonium tungstate national standard to meet the index requirements in electronic and catalyst industries, and the preparing method can be used for producing high purity tungsten powder and tungsten metal products with purity higher than 4N (99.99%). The preparation method of the invention has a simple operation, the quality of the ammonium tungstate products prepared by the method is stable, and the crystallization rate could be higher than 96%.

Description

A kind of preparation method of ultrapure ammonium tungstate
Technical field
The present invention relates to the preparation method of ultrapure ammonium tungstate, particularly produce a kind of preparation method of the required ultrapure ammonium tungstate raw material of high purity tungsten, high purity tungsten metal products, high reactivity tungsten-based catalyst.。
Background technology
Ammonium tungstate can be used for producing lubricant, inhibiter, pigment, fertilizer, catalyzer; Can also be used to produce WO 3With the W powder, and then be processed into tungsten metal productss such as tungsten rod, tungsten crucible, tungsten filament, tungsten bar, tungsten electrode, tungsten slab, tungstenalloy; In addition; Also be applied to industries such as super capacitor, nano material, photovaltaic material, superconducting material, hydrogen storage material, fuel cell, be widely used in fields such as iron and steel, wimet, metal processing, electronic devices and components, electric light source, electrovacuum, metallurgy, chemical, medicine bioengineering, aerospace and military project industry.
The method of producing ammonium tungstate at present mainly contains neutralisation, evaporation, extraction and ion-exchange; Industrial preparation ammonium tungstate mainly is to adopt evaporation; Even the method for evaporative crystallization again after dissolving in ammoniacal liquor with many ammonium tungstates raw material of industrial seconds; Promptly earlier ammonium tungstate is carried out ammonia in stainless steel stirring axe and dissolve, reaction equation is:
（NH 4） 2O·4WO 3·2H 2O?+?6NH 4OH?=?4（NH 4） 2WO 4?+?5H 2O
H 2WO 4?+ 2NH 4OH?=（NH 4） 2WO 4?+?2H 2O
The reaction technology condition is: according to many ammonium tungstates (kg): pure water (l): ammoniacal liquor (l)=1: (1 ~ 1.1): 0.5 is reinforced, and stir speed (S.S.) be (70 ~ 80) r/min, and temperature condition be (60 ~ 75) ℃, the molten (NH afterwards of ammonia 4) 2WO 4Solution density is controlled near 1.16 ~ 1.28g/cm 3, in solution PH=8.0 ~ 11.0 scopes.And then solution is carried out evaporative crystallization with steam, reaction equation is:
7（NH 4） 2WO 4?+?8H 2O?=?3（NH 4） 2O·7WO 3·4H 2O↓+?8NH 4OH
NH 4OH?=?NH 3↑?+?H 2O
The technical qualification of this reaction are: vapor pressure is 0.10 ~ 0.19Mpa, and in order to keep solution boiling in the axe, keeping free ammonia in the evaporative process is (4 ~ 6) g/L, and mother liquor density is controlled at (1.16 ~ 1.28) g/cm 3, the final PH=7.0 of solution ~ about 7.7.Filter (not dissolving impurity such as thing) behind the crystallisation by cooling in order to remove part.When high, the percent crystallization in massecuite of product generally is not higher than 90% under these processing condition to purity requirement; When the purity generalized case was required, its product percent crystallization in massecuite maintained in (90 ~ 95) % scope (repair referring to Zhang Qi and wait chief editor's " tungsten metallurgy ", metallurgical industry press was the 147th page in 2005).
In view of many ammonium tungstates carry out ammonia when dissolving liquid-solid ratio relatively large; Evaporation time is long; Will some impurity (like iron etc.) be brought in the ammonium tungstate because of ammonium tungstate solution long-time stirring in the stainless steel reaction axe like this; In addition, and also owing to the malconformation of thermograde, basicity mass transfer causes the different crystal grain peritectoids that caused of ammonium tungstate fine particle growth speed, wraps up in the trichite life, thereby cause impurity to be carried secretly; Reduced the purity of tungstate product; Make the product purity produced be difficult to surpass ammonium tungstate national standard (GB/T 10116-2007) zero level, or even be difficult to surpass ammonium tungstate national standard (GB/T 10116-2007) one-level, can't satisfy in the fields such as growing electronic industry, chemical industry are synthetic, oil catalysis demand high-purity, ultrapure ammonium tungstate.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of ultrapure ammonium tungstate.
For realizing above-mentioned purpose; Technical scheme of the present invention is: be the basis with the prior art; Adopting Tungsten oxide 99.999, ammonium metawolframate, the ammonium paratungstate of ammonium tungstate national standard (GB/T 10116-2007) secondary (MSA-2), one or more tungsten sources of many ammonium tungstates is raw material, adds pure water and carries out with liquefied ammonia (or ammoniacal liquor) normal temperature that ammonia is molten, stirring and evenly mixing, need not extra-heated; And carry out the heavy crystallization of acid after add super acids down in normal pressure behind the abstraction impurity removal; Carry out solid-liquid separation after the heavy end of acid, the ammonium tungstate after separating is implemented oven dry, the moisture content in ammonium tungstate is reduced to≤1.08g/cm 3
Method of the present invention be carry out ammonia when dissolving batching in the control solution main body tungsten ion concentration at 50 ~ 300g/L; The main body solution PH remains in 7.5 ~ 11.0 useful ranges before the heavy crystallization of control acid simultaneously; Earlier through abstraction impurity removal, adopt super acids to carry out the heavy crystallization of acid when acid is heavy before acid is heavy, the heavy terminal point PH of acid is controlled at 4.0 ~ 7.0; The finished product percent crystallization in massecuite surpasses 96%; Prepared tungstate product purity far surpasses ammonium tungstate national standard (GB/T 10116-2007) zero level classification, has satisfied the index request of electronic industry, catalyzer industry, and can be used for production purity 4N (99.99%) above high purity tungsten and tungsten metal products.
The present invention compared with prior art, because of before adopting acid heavy in advance through abstraction impurity removal, it is heavy by super acids ammonium tungstate solution have been carried out the controlled acid of conditionality when acid is heavy; Thereby make the product percent crystallization in massecuite high; The super acids consumption is few and the residual tungsten recovery rate high, and the impurity amount of bringing into is few, and working method is simple; Constant product quality, technical matters is reliable.
The present invention has avoided adopting fire coal or combustion gas heating to produce the approach of steam to the ammonium tungstate solution evaporative crystallization, has found the novel method of the ultrapure ammonium tungstate of a kind of cleaner production, not only green but also environmental protection, low-carbon (LC), and process stabilizing, reliable product quality.
Embodiment:
Implement row 1: one or more tungsten sources of getting Tungsten oxide 99.999 that the 300kg technical qualification meet ammonium tungstate national standard (GB/T 10116-2007) secondary (MSA-2), ammonium metawolframate, ammonium paratungstate, many ammonium tungstates are raw material; Add pure water and carry out with liquefied ammonia (or ammoniacal liquor) normal temperature that ammonia is molten, stirring and evenly mixing; Need not extra-heated, tungsten ion concentration was at 240g/L in the control solution main body when ammonia dissolved batching, and the main body solution PH remains in 9.0 ~ 11.0 useful ranges before the heavy crystallization of control acid simultaneously; Then in advance through abstraction impurity removal; Under normal pressure, add super acids then and carry out the heavy crystallization of acid, the heavy terminal point PH of acid is controlled at 6.0 ~ 7.0, carries out solid-liquid separation behind sour heavy the end; Ammonium tungstate after separating is implemented oven dry 1 ~ 2h, and the moisture content in ammonium tungstate is reduced to≤1.08g/cm 3, the finished product percent crystallization in massecuite surpasses 96%, and prepared tungstate product purity surpasses ammonium tungstate national standard (GB/T 10116-2007) zero level classification, and its quality and technical index is as shown in table 1.
Table 1
Element Al Bi Ca Co Cr Cu Cd Fe Mg Mn
Content (%) ＜0.0002 ＜0.00005 ＜0.0003 ＜0.0003 ＜0.0003 ＜0.0001 ＜0.00005 ＜0.0003 ＜0.0002 ＜0.0002
Element Ni Sb Si Sn Ti V As Pb Na S
Content (%) ＜0.0002 ＜0.0001 ＜0.0003 ＜0.00005 ＜0.0001 ＜0.0003 ＜0.0004 ＜0.00005 ＜0.0003 ＜0.0003
Element Mo K P ? ? ? ? ? ? ?
Content (%) ＜0.0002 ＜0.0004 ＜0.0003 ? ? ? ? ? ? ?
Implement row 2: one or more tungsten sources of getting Tungsten oxide 99.999 that the 300kg technical qualification meet ammonium tungstate national standard (GB/T 10116-2007) secondary (MSA-2), ammonium metawolframate, ammonium paratungstate, many ammonium tungstates are raw material; Add pure water and carry out with liquefied ammonia (or ammoniacal liquor) normal temperature that ammonia is molten, stirring and evenly mixing; Need not extra-heated, tungsten ion concentration was at 160g/L in the control solution main body when ammonia dissolved batching, and the main body solution PH remains in 8.0 ~ 10.0 useful ranges before the heavy crystallization of control acid simultaneously; Then in advance through abstraction impurity removal; Under normal pressure, add super acids then and carry out the heavy crystallization of acid, the heavy terminal point PH of acid is controlled at 5.0 ~ 6.0, carries out solid-liquid separation behind sour heavy the end; Ammonium tungstate after separating is implemented oven dry 1 ~ 2h, and the moisture content in ammonium tungstate is reduced to≤0.90g/cm 3, the finished product percent crystallization in massecuite surpasses 96.3%, and prepared tungstate product purity surpasses ammonium tungstate national standard (GB/T 10116-2007) zero level classification, and its quality and technical index is as shown in table 2.
Table 2
Element Al Bi Ca Co Cr Cu Cd Fe Mg Mn
Content (%) ＜0.0002 ＜0.00005 ＜0.0003 ＜0.0003 ＜0.0003 ＜0.0001 ＜0.00005 ＜0.0003 ＜0.0002 ＜0.0002
Element Ni Sb Si Sn Ti V As Pb Na S
Content (%) ＜0.0002 ＜0.0001 ＜0.0003 ＜0.00005 ＜0.0001 ＜0.0003 ＜0.0004 ＜0.00005 ＜0.0003 ＜0.0003
Element Mo K P ? ? ? ? ? ? ?
Content (%) ＜0.0002 ＜0.0004 ＜0.0003 ? ? ? ? ? ? ?
Implement row 3: one or more tungsten sources of getting Tungsten oxide 99.999 that the 300kg technical qualification meet ammonium tungstate national standard (GB/T 10116-2007) secondary (MSA-2), ammonium metawolframate, ammonium paratungstate, many ammonium tungstates are raw material; Add pure water and carry out with liquefied ammonia (or ammoniacal liquor) normal temperature that ammonia is molten, stirring and evenly mixing; Need not extra-heated, tungsten ion concentration was at 50g/L in the control solution main body when ammonia dissolved batching, and the main body solution PH remains in 7.5 ~ 9.0 useful ranges before the heavy crystallization of control acid simultaneously; Then in advance through abstraction impurity removal; Under normal pressure, add super acids then and carry out the heavy crystallization of acid, the heavy terminal point PH of acid is controlled at 4.0 ~ 5.0, carries out solid-liquid separation behind sour heavy the end; Ammonium tungstate after separating is implemented oven dry 1 ~ 2h, and the moisture content in ammonium tungstate is reduced to≤0.85g/cm 3, the finished product percent crystallization in massecuite surpasses 96.5%, and prepared tungstate product purity surpasses ammonium tungstate national standard (10116-2007) zero level classification, and its quality and technical index is as shown in table 3.
Table 3
Element Al Bi Ca Co Cr Cu Cd Fe Mg Mn
Content (%) ＜0.0002 ＜0.00005 ＜0.0003 ＜0.0003 ＜0.0003 ＜0.0001 ＜0.00005 ＜0.0003 ＜0.0002 ＜0.0002
Element Ni Sb Si Sn Ti V As Pb Na S
Content (%) ＜0.0002 ＜0.0001 ＜0.0003 ＜0.00005 ＜0.0001 ＜0.0003 ＜0.0004 ＜0.00005 ＜0.0003 ＜0.0003
Element Mo K P ? ? ? ? ? ? ?
Content (%) ＜0.0002 ＜0.0004 ＜0.0003 ? ? ? ? ? ? ?

Claims (9)

1. the preparation method of a ultrapure ammonium tungstate; Comprise that employing is a raw material with Tungsten oxide 99.999, ammonium metawolframate, ammonium paratungstate, many ammonium tungstates etc.; Add pure water and carry out with liquefied ammonia (or ammoniacal liquor) normal temperature that ammonia dissolves, stirring and evenly mixing, need not extra-heated, behind abstraction impurity removal, add super acids down and carry out acid and sink crystallization in normal pressure; Acid is carried out solid-liquid separation after sinking and finishing, and the ammonium tungstate after separating is implemented to get this product after the oven dry.It is characterized in that: carry out ammonia when dissolving batching in the control main body solution tungstate ion concentration at 50 ~ 250g/L.
2. the method for the ultrapure ammonium tungstate of preparation according to claim 1 is characterized in that: adopt liquefied ammonia to carry out ammonia and dissolve, the heat of emitting when utilizing liquefied ammonia (or ammoniacal liquor) ammonia to dissolve dilution is carried out self-constant temperature holding temperature balance, need not extra-heated.
3. the method for the ultrapure ammonium tungstate of preparation according to claim 1 is characterized in that: the raw material of employing is any or multiple in Tungsten oxide 99.999, ammonium metawolframate, ammonium paratungstate, the many ammonium tungstates etc.
4. the method for the ultrapure ammonium tungstate of preparation according to claim 1 is characterized in that control main body solution PH remains on 7.5 ~ 11.0 when carrying out the molten batching of ammonia.
5. the method for the ultrapure ammonium tungstate of preparation according to claim 1 is characterized in that in that to adopt super acids to carry out acid necessary first through extraction agent abstraction impurity removal (especially impurity negatively charged ion) cleansing soln before heavy.
6. the method for the ultrapure ammonium tungstate of preparation according to claim 1 is characterized in that when adopting super acids to carry out the heavy crystallization of acid acid sinks terminal point PH and be controlled at 4.0 ~ 7.0.
7. the method for the ultrapure ammonium tungstate of preparation according to claim 1 is characterized in that when going sour sinking, and adopts super acids to carry out the heavy crystallization of acid, and percent crystallization in massecuite surpasses 96%, and prepared tungstate product steady quality.
8. the method for the ultrapure ammonium tungstate of preparation according to claim 1 is characterized in that: prepared ammonium tungstate purity far surpasses ammonium tungstate national standard (GB/T 10116-2007) zero level classification.
9. the method for the ultrapure ammonium tungstate of preparation according to claim 1; It is characterized in that: prepared ammonium tungstate purity satisfies the index request of electronic industry, catalyzer industry, and can be used for production purity 4N (99.99%) above high purity tungsten and tungsten metal products.
CN2011100882003A 2011-04-09 2011-04-09 A preparing method for an ultra-pure ammonium tungstate Pending CN102730759A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942222A (en) * 2012-10-28 2013-02-27 孙世凡 Method for preparing ammonium tungstate by treating waste tungsten oxide
CN106756124A (en) * 2016-11-25 2017-05-31 桂林理工大学 A kind of separating potassium from ammonium paratungstate, sodium, sulphur, the method for chlorine impurity
CN111283211A (en) * 2020-02-26 2020-06-16 厦门虹鹭钨钼工业有限公司 Preparation method of high-purity tungsten powder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942222A (en) * 2012-10-28 2013-02-27 孙世凡 Method for preparing ammonium tungstate by treating waste tungsten oxide
CN106756124A (en) * 2016-11-25 2017-05-31 桂林理工大学 A kind of separating potassium from ammonium paratungstate, sodium, sulphur, the method for chlorine impurity
CN111283211A (en) * 2020-02-26 2020-06-16 厦门虹鹭钨钼工业有限公司 Preparation method of high-purity tungsten powder

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Application publication date: 20121017