Ammonium Paratungstate Hydrates and Ammonium Paratungstate Decahydrate

The invention is directed to ammonium paratungstate decahydrate containing at least 75% of crystals having a length of at least 200 μm and having a ratio of length to width of less than 4.5:1.
 
The present invention relates to a novel process for preparing highly pure ammonium paratungstate hydrates and ammonium paratungstate decahydrate having a selected crystal structure.
 
Ammonium paratungstate hydrates (hereinafter referred to as APTs) are known intermediates for producing tungsten metal, tungsten-containing catalysts or hard materials based on tungsten, for example tungsten carbides.
 
The preparation of highly pure APT is carried out essentially via acid or alkali digestion or fusion of tungsten-containing concentrates or tungsten scrap with subsequent purification stages involving precipitation processes and liquid-liquid extraction. The purified solution is generally concentrated by evaporation, resulting in APT finally crystallizing out. The publication “Kristallographische Untersuchung der Ammoniumparawolframate (Zeitschrift für Kristallographie, vol. 120, pp. 216-228 (1964))” by M. Hähnert states that APT×10H2O is formed on slow evaporation of an ammonium tungstate solution prepared from WO3 and NH3 solution. The crystals have an acicular morphology. The bulk density of the product is 0.7 g/cm3. This is not an industrial process but a preparative laboratory process.
 
Further routes to the preparation of APT×10H2O are described in the article “Characterisation of various commercial forms of ammonium paratungstate powder, Journal of Material Science, No. 10 (1975), pages 571-577”.
 
In one process variant, an ammonium tungstate solution prepared from tungstic acid and an excess of NH3 solution is subject to freeze drying. The product formed has a crumbly poorly defined crystal morphology and the bulk density is 1.03 g/cm3. In a second process variant, an ammonium tungstate solution prepared as described above is slowly neutralized with HCl solution at room temperature. The acicular crystals formed have a length of 16-70 μm and a width of 2-14 μm and the bulk density is 1.46 g/cm3. Both processes form APT×10H2O having a low bulk density and the necessary product purity can be achieved only when using clean tungstic acid. In addition, a freeze drying procedure in one case and the use of clean HCl solution in the other case leads to very high process costs. When HCl is used, the product is contaminated with chloride as a result of the process.
 
In the specialist book “Metallurgie der seltenen Metalle, Seligman, Krejn and Samsonov (1978), Metallurgia publishers (USSR), pp. 62-63”, an industrial process for preparing APT×10H2O is described as follows. Scheelite concentrate is digested with HCl solution at 90-100° C. so as to form tungstic acid. The tungstic acid is subsequently dissolved in NH3 solution and the solution is cooled. The resulting ammonium tungstate solution is slowly neutralized with HCl solution to a pH of 7.3-7.4 while stirring. After allowing to stand for 24 hours, the APT×10H2O product is separated off. The acicular crystals have a length of 15-25 μm and a width of 1-3 μm and the bulk density is 0.98 g/cm3. The crystallization yield here is 85-90%. This product still contains considerable amounts of impurities. A further disadvantage of this process is the high consumption of clean HCl solution and the large amount of W-containing NH4Cl solution (mother liquor) which has to be worked up.

Thermal Decomposition Process of Ammonium Paratungstate

Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes.
 
The reaction is usually endothermic as heat is required to break chemical bonds in the compound undergoing decomposition. If decomposition is sufficiently exothermic, a positive feedback loop is created producing thermal runaway and possibly an explosion.
 
Examples
Calcium carbonate (limestone or chalk) decomposes into calcium oxide and carbon dioxide when heated. The chemical reaction is as follows:
CaCO3 → CaO + CO2
The reaction is used to make quick lime, which is an industrially important product.
Engraving of assorted scientific equipment, such as a pneumatic trough. A dead mouse rests under one glass canister.
Some oxides, especially of weakly electropositive metals decompose when heated to high enough temperatures. A classical example is the decomposition of mercuric oxide to give oxygen and mercury metal. The reaction was used by Joseph Priestley to prepare samples of gaseous oxygen for the first time.
When water is heated to well over 2000 °C, a small percentage of it will decompose into OH, monotomic oxygen, monotomic hydrogen, O2, and H2.
The compound with the highest known decomposition temperature is carbon monoxide at ≈3870 °C (≈7000 °F).
 
Decomposition of nitrates, nitrites and ammonium compounds
Ammonium dichromate on heating yields nitrogen, water and chromium(III) oxide.
Ammonium nitrate on strong heating yields dinitrogen oxide ("laughing gas") and water.
Ammonium nitrite on heating yields nitrogen gas and water.
Barium azide on heating yields barium metal and nitrogen gas.
Sodium nitrate on heating yields sodium nitrite and oxygen gas.
 
Ease of decomposition
When metals are near the bottom of the reactivity series, their compounds generally decompose easily at high temperatures. This is because stronger bonds form between atoms towards the top of the reactivity series, and strong bonds break less easily. For example, copper is near the bottom of the reactivity series, and copper sulfate (CuSO4), begins to decompose at about 200 °C, increasing rapidly at higher temperatures to about 560 °C. In contrast potassium is near the top of the reactivity series, and potassium sulfate (K2SO4) does not decompose at its melting point of about 1069 °C, nor even at its boiling point.
 
The thermal decomposition of ammonium paratungstate in different atmosphere is discussed. The thermal decomposition is characterized by four steps,including crystal water release,ammonia leaving behind anamorphous compounds,ammonium tungsten bronze formation,WO3 crystallization. The decomposition of ammonium paratungstate plays an important role on tungsten powder particle by conducting the industrial production of different particle size of tungsten powder.

 

Tungsten Carbide Ball V-shaped Groove Grinding Process

The specific requirements of each procedure of tungsten carbide polished ball as follow: Coarse grinding at the beginning, machined by vertical steel ball machine and uses 100# diamond resin grinding wheel (grain size is 100). Before the grinding, the grinding wheel to be ball milled with the corresponding specifications of the groove. In addition, the groove depth is generally equal to 1/5-1/3 of tungsten carbide polished ball and runout groove should ensure that within 0.03mm.

Then the fine grinding, which also machined on vertical steel ball grinding machine and uses 150# diamond grinding wheel (the grain size is 150, finer suitable for fine grinding). It is similar to coarse grinding, the grinding wheel to be ball milled with the corresponding specifications of the groove. The groove depth is generally equal to 1/5-1/3 of tungsten carbide polished ball and runout groove should ensure that within 0.03mm.

The next is coarse pestle, which uses grinding plate for machining on vertical steel ball machine. The lower grinding plate opening 90 ° symmetrical V-groove, milled plate installation alignment groove runout less than 0.02mm. Before the grinding, the groove should be pre-grinding by the standard ball, which adopts concentration 30% grinding fluid and 140/170# SiC (grain size is 140/170) as grinding compound. Disposable add a little abrasive, with a smaller flow, pressure control in 4KN-6KN, speed 25-30r / min, grinding to a balance of + 0.03mm-0.04mm, 0.001mm in control of roundness, approved changes in diameter assurance within 0.002mm, the surface roughness of less than Ra0.4.

Tungsten Carbide Ball V-shaped Groove Grinding Process II

After coarse pestle, it should be fine pestle on vertical steel ball machine. It uses grinding plate as grinding tool and the lower grinding plate opening 90 ° symmetrical V-groove, milled plate installation alignment groove runout less than 0.02mm, which groove also should be pre-grinding by standard ball to ensure the precision.

Afterwards, tungsten carbide ball should be polished by vertical lathe and uses oak plate as grinding tool to turn arc groove with 0.5R. It has grooved boards with four claw chuck clamping, alignment grooves within 0.1mm, with W5 / W7 diamond paste (Old GB model, or about 4000 mesh / 3000 mesh) as a polishing paste, applied to certain pressure on the grinding plate does not move, speed control in 60r / min, the polishing process can be carried out for 4-6 hours, making the ball appear like a mirror.

Finally, cooling tungsten carbide polished ball about 5min. Then use kerosene to remove the stains on the surface and wipe out by clean cloth. Testing and packaging: The amount of change in the diameter of the grant requested diameter ball is detected using a micrometer or ruler for detecting extremely; roundness detected; the surface roughness using observation and comparison assay. It is required soft cushion apart between the balls and the ball use soft cushion apart, to prevent the collision of the balls and the ball, so that it is deformed or worn.

tungsten carbide ball

 

Reduction of Ammonium Paratungstate Generated during Hydrometallurgical Processing of Tungsten-Copper Borings

Reduction of Ammonium Paratungstate Generated during Hydrometallurgical Processing of Tungsten-Copper Borings

Ammonium paratungstate (or APT) is a white crystalline salt of ammonium and tungsten, with the chemical formula (NH4)10(H2W12O42)·4H2O.
 
Ammonium paratungstate is produced by separating tungsten from its ore. Once the ammonium paratungstate is prepared, it is heated to its decomposition temperature, 600 °C. Left over is WO3, tungsten(VI) oxide. From there, the oxide is heated in an atmosphere of hydrogen, reducing the tungsten to elemental powder, leaving behind water vapor. From there, the tungsten powder can be fused into any number of things, from wire to bars to other shapes.


Tungsten-copper (W-Cu) alloy is employed for manufacturing heavy duty contactors, relays,switches etc. During production of such components, W-Cu turnings/borings are generated. At CSIR-NML, a process for recovering tungsten and copper from tungsten-copper borings containing 46.01% W, 53.78% Cu, 0.13% Fe and other minor metals as high purity tungsten powder and copper powder has been developed. In the present work, a detailed investigation on reduction of ammonium paratungstate (APT) having purity 99.95% by hydrogen gas to produce high purity tungsten powder is presented. The various process parameters such as temperature, time and flow rate of hydrogen gas have been optimized. At the temperature of 800°C and 0.1 l pm flow rate a reduction of 77.78% was observed up to 2h time. At 900°C, with increase in flow rate from 0.1 l pm to 0.3lpm the increase in reduction was found to be from 63.88% to 99.99% at 1h time.At still high temperature of 1000°C, almost complete reduction was obtained at 0.1 l pm flow rate in 1h time. The effect of bed-depth was also carried out. At all temperatures chemical reaction was the rate determining step.

APT

 

 

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