Ammonium metatungstate decomposition temperature is the temperature of AMT coming out decomposition reaction; while in the actual production environment, ammonium metatungstate will have several different decomposition temperatures according to complete reaction or not. Decomposition temperature of a substance means the temperature at which the substance chemically decomposes, which the chemical decomposition caused by heat. 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.

 

Ammonium metatungstate will produce different products at different decomposition temperatures. When the heat treatment temperature is 200~300°C, AMT will be removed of all crystal water and most of the ammonium ions; then phase transformation will occur at 300-350°C to generate metastable tungsten oxide species; when the heat treatment temperature rise to 500~550°C, a small amount of ammonium and bound water is still not broken down; and when the temperature rises to 600°C and above, ammonium metatungstate will completely decomposed into tungsten trioxide (WO₃); when the temperature raised to 700°C and held for 2 hours, mesoporous tungsten trioxide hollow balls will be obtained.

 

About ammonium metatungstate:

Ammonium metatungstate (AMT) is an important intermediate compound in tungsten wet smelting process, with the appearance of white or slightly yellow crystalline, the biggest solubility in all the tungsten compound, wherein the solubility will bigger than 300g WO₃/100ml H₂O at 25℃. The preparation methods of ammonium metatungstate are mainly Acid neutralization, Thermal separation, electrodialysis, solvent extraction and ion exchange method and the method depends on ammonium paratungstate (APT). AMT is the important raw material of tungsten compound (such as tungsten trioxide, blue tungsten oxide, tungsten hexachloride ect.); at the same time, it is usually used in industries of petroleum, chemical, ceramic, lubrication and so on; in addition, since the continually developing of electronics industry and the constantly mining of new material, AMT is also used in film substrate, capacitor and shielding ect. of semiconductor devices.

Ammonium metatungstate spray drying tower belongs to the spray equipments of ammonium metatungstate production, which is the most widely used of liquid forming process and drying industry. Spray-drying tower is suitable for preparing powder, granular solid product from liquid raw material with forms of suspoemulsions, solution, emulsion, and paste. Thus, when the finished product particle size distribution, residual moisture content, bulk density and particle shape are in line with the precision standard, the spray drying tower is supposed to be an ideal drying process.

 

Principle of ammonium metatungstate spray drying tower is that the air goes into the top dryer’ air distributor after filtered and heated, then the hot air will uniformly go into the drying room in the spiral. AMT feed solution through the high-speed centrifugal atomizer (rotary) at the top of the tower to be sprayed into the extremely fine mist liquid beads AMT, and dried AMT will come into being in a very short time when it in contacts with the stream of hot air. Then, ammonium metatungstate is exported continuously from the bottom of the spray drying tower and the cyclone, and the exhaust gases are vented by the fan.

 

Extended reading:

Spray drying tower is the equipment which can be used in drying biological pesticide, medicine and food microorganism, with the max evaporation rate of 10 kg/h, max gas drying rate of 150 kg/h; the main function of a spray drying tower is to dry the materials in solution state in it and then discharge in form of solid. There are 6 properties of a spray drying tower which show bellows:

1. The fast drying speed within seconds to finish;

2. Suitable for the heat-sensitive materials;

3. Widely apply in most of products with very huge difference;

4. The outlet product has excellent dispersion, fluidity and solubility;

5. Sample producing process and easy to operate and control;

6. The part which in contact with material is using stainless steel to protect raw material not to be polluted and extend the service life of the equipment.

The detection methods of ammonium metatungstate are graphite furnace atomic absorption spectrometry (GFAAS), flame atomic absorption spectrometry (FAAS), inductively coupled plasma emission spectrum (ICP-MS) and coprecipitation separation - hydride atomic fluorescence spectrometry (i.e. coprecipitation separation - HG - AFS method.

 

Graphite furnace atomic absorption spectrometry (GFAAS) is the method absorbing and analyzing atoms by atomization with current heating in an atomization device which produced by graphite and to form shapes of tubes, cups and others. Since all atoms of sample are getting involved in the atomization, and the atomic concentration diluted in the flame gas has been avoided, then the analytical sensitivity has been greatly improved. While, when that method applied in detecting trace metal element, its property is better than many of other methods, and will be used in analysis of small amount samples and detect analysis of solid sample.

 

Detection equipments of ammonium metatungstate are atomization device, flame atomic absorption spectrometer, and inductively coupled plasma mass spectrometer ect..

1. Atomization device is a device for sample atomization of atomic absorption spectrometry, which is used in both graphite furnace atomic absorption spectrometry (GFAAS) and flame atomic absorption spectrometry (FAAS). It converts the sample to a free atomic vapor (ground state atom) to absorb the characteristic radiation, and to calculate the element to be measured. There are many kinds of atomizers, and they can be divided into two categories of fire stuffing atomizer and electrothermal atomizer in common. The former includes pre-mixed and full consumption type; the latter includes graphite furnace, carbon wire atomizer, carbon rod atomizer, graphite increase exhaust, and graphite probes ect.;

2. Inductively coupled plasma mass spectrometer consists of plasma torch (composed of three concentric quartz tube), high frequency generator (to produce high frequency current), induction coil, gas supply system and atomization system and other parts;

3. Flame atomic absorption spectrometer is composed of light source, atomization system, spectroscopic system and detection system. The principle is that the instrument emits light with the characteristic spectral line of the element to be measured from the light source, then when the sample vapor passes through, the light will be absorbed by the under measure ground state atom, and finally measured by the weakened degree of radiation characteristic spectrum of light.

Ammonium metatungstate production equipment according to the different stages of production and different methods may be variety, such as pyrolysis method of AMT production, a reactor, rotary kiln, high-speed centrifugal spray drying equipment or spray atomization drying equipment may be used; In addition, other pyrolysis equipments include microwave oven, plate multiple hearth furnace and tubular multiple hearth furnace. The direct recovery AMT can be more than 95% when using tubular multiple hearth furnace.

 

At present, the pyrolysis equipment for producing ammonium metatungstate is mainly rotary calciner, which is a rotary kiln. A rotary kiln is a pyroprocessing device used to raise materials to a high temperature (calcination) in a continuous process. The kiln is a cylindrical vessel, inclined slightly to the horizontal, which is rotated slowly about its axis. The material to be processed is fed into the upper end of the cylinder. As the kiln rotates, material gradually moves down towards the lower end, and may undergo a certain amount of stirring and mixing. Hot gases pass along the kiln, sometimes in the same direction as the process material (co-current), but usually in the opposite direction (counter-current). The hot gases may be generated in an external furnace, or may be generated by a flame inside the kiln. Such a flame is projected from a burner-pipe (or "firing pipe") which acts like a large bunsen burner. The fuel for this may be gas, oil, pulverized petroleum coke or pulverized coal. 

Ammonium metatungstate produced by ion exchange method will probably use ion exchange resin, crystallizer, or spray dryer and other production equipments. Alkali decomposition furnace is mainly used for decomposing tungsten ore during the preparation of AMT to dissolve tungsten into a solution. A plate and frame filter press is the most fundamental design, and many now refer it as a "membrane filter plate". This type of filter press consists of many plates and frames assembled alternately with the supports of a pair of rails. It is used for the impurity removal process of sodium tungstate for preparing high purity sodium in the APT preparation.

Ion exchange colum is used for removal of S, Mo, P, As, Ca, Cu and Sn and other impurities. Co-current deionization refers to the original downflow process where both input water and regeneration chemicals enter at the top of an ion exchange column and exit at the bottom. Co-current operating costs are comparatively higher than counter-current deionization because of the additional usage of regenerants. Because regenerant chemicals are dilute when they encounter the bottom or finishing resins in an ion exchange column, the product quality is lower than a similarly sized counter-flow column. Spray drying is a method of producing a dry powder from a liquid or slurry by rapidly drying with a hot gas. This is the preferred method of drying of many thermally-sensitive materials such as foods and pharmaceuticals.

The surface decarburized WC-Co gradient cemented carbide based on impregnation liquid of ammonium metatungstate solution (AMT) can greatly enhance the comprehensive performance of cemented carbide; and with the simple process, easy to operate, it is suitable for industrial production. The preparation steps are as follows: 

1. Put the conventional WC-Co carbide under vacuum conditions at 100~500°C for dewaxing, then to carry out presintering in 800~900°C to obtain presintering billet with a certain strength and porosity; 

2. After them, the sample is dipped into ammonium metatungstate solution to form concentration gradient of AMT with a certain depth and distribution from the surface layer to the inner; 

3. Then, after the sample is dried, put it in vacuum furnace for sintering along with slow heating in low temperature stage, to make the ammonium metatungstate decomposed, which the broken down products (tungsten oxide) will react with surface substance of WC, Co, then we can get surface decarburized WC-Co gradient cemented carbide. 

 

Cemented carbide is a kind of metal ceramic tool material which prepared by powder metallurgy method by taking refractory metal compounds (such as WC, TiC, TaC, NbC, etc.) as the matrix, and transition of metals (like Co, Fe and Ni) as bonding phase. Due to its high strength, hardness and elastic modulus, wear resistance, corrosion resistance, low thermal expansion coefficient and stable chemical properties, etc, it in has important application in metal cutting, wood processing, oil drilling in mines, composite materials processing and other respects. Conventional class of WC-Co carbide is uniformly consisted with two phases of WC and binding phase, however it exists contrary relationship between the hardness, wear resistance and strong toughness. The WC - Co gradient cemented carbide structure with high wear-resistance and hardness surface, toughness core part was developed in the 1980s, while the appearance of surface decarburized WC-Co gradient cemented carbide makes it easier to control surface eta phase formation depth, and thereby to prepare the superior performance of WC-Co carbide. 

It is found that the supported ammonium metatungstate (AMT) catalysts with the carriers of silicon dioxide, titanium dioxide and aluminium oxide have exhibited good catalytic activity for the synthesis of ortho - light anisole by gas - phase reaction of catechol and methanol. Among them, the AMT / silicon dioxide catalyst with tungsten loading of 7.9% has the best catalytic performance; in addition, the species with weak acidity and alkalinity which formed by the partial decomposition of ammonium metatungstate in the calcination process has been indicated to be the active center of the catalytic reaction.


 

Preparation of silicon dioxide supported ammonium metatungstate catalyst is using the traditional impregnation method, which is dipping carrier of silicon dioxide with ammonium metatungstate (AMT) aqueous solution in equal volume, followed by drying at 363 K for 6 hours, and then calcining at a certain temperature for 3 hours under air atmosphere to obtain SiO₂/AMT catalyst. The study found that the calcination temperature affects the catalytic activity of silicon dioxide supported ammonium metatungstate catalyst; while the catalysts obtained at calcination temperatures of 533K and 573K showed the highest catechol conversion rate and selectivity of adjacent hydroxyl benzene methyl ether within 10 hours, which is respectively maintaining at about 97% and 90%.

 

Moreover, with the extension of reaction time, the activity of silicon dioxide supported ammonium metatungstate catalyst is decreased slowly, which is mainly attributed to the carbon deposition on the catalyst. The study of regeneration of deactivated SiO₂ / AMT catalyst has proved that both the alcohol washed purging and low temperature (533k) calcination could not obviously restore the activity of the catalyst, and also the regenerated catalyst has stability no better than the fresh catalyst. This may be due to the change of the properties (including the acidity and alkalinity) of active centers on catalyst surface after high temperature regeneration treatment, and to make the easier deactivation of regenerated catalyst.

In recent years, solid acid alkali catalysis of gas-solid-phase reaction of alkylation of catechols has attracted attention due to the environmentally friendly economy and overcoming the environmental pollution, separation and recovery difficulties and equipment corrosion and other defects, compared to conventional synthesis methods, and has shown significant advantages in saving resources and improving economic efficiency. It is found that Al-Ti-P-O, Al-Ti-Si-P-O and silica-supported ammonium metatungstate (AMT/SiO₂) catalyst exhibited high catalytic activity.

 

Hydrotalcite is a kind of anionic clay with layered structure, because of its special layered structure and high catalytic performance in acid-base catalysis, condensation, addition polymerization, hydrogenation and alcohol conversion reaction, hydrotalcite has attracted many concerns. The exchangeable property of hydrotalcite anions make all kinds of anions (such as metatungstate ion) can be introduced into the interlayer of hydrotalcite in succession, thus to form a large class of materials - pillared hydrotalcite layered material.

 

A study has pointed out a preparation method of ammonium metatungstate hydrotalcite catalyst, and studied its catalytic performance, while the preparation steps are as follows:

1. synthesis of hydrotalcite material, take the raw material of magnesium nitrate hexahydrate, aluminum nitrate and sodium hydroxide, and to control the final pH value among 8 ~ 10 of the system, then go on aging, filtration and washing to get hydrotalcite NO₃-MgAl;

2. Weigh a certain amount of fresh prepared hydrotalcite NO₃-MgAl to disperse in distilled water, stirring at room temperature for overnight to fully expand;

3. Add dilute nitric acid dropwise to adjust the pH value of hydrotalcite slurry among 5.5~6, then rise the temperature to 348K;

4. Rapidly add ammonium metatungstate solution under the condition of stirring, and to react at 348K for 2 to 3 hours, then pumping wash the sample and dry at 348K to get the ammonium metatungstate hydrotalcite catalyst, i.e. AMT-Mg₂Al.

The results showed that after changed with AMT, hydrotalcite will exhibit activity to the reaction of gas-solid phase reaction of catechol and methanol, while the conversion of catechol is 75%, the selectivity of guaiacol is 90%, but the catalytic activity decays.