MnOx/WO3/TiO2 Denitration Catalyst

SCR denitration catalystThe better reacting temperature of tungsten trioxide SCR denitration catalyst is about 300~400℃, however, it is no way to achieve this range in the general factory; therefore, the flue gas should be heated by the GGH or burners in the denitration process, thus cause the energy consumption and operating costs increased. So, it is imperative to reducing the suitable temperature of denitration catalyst and improving its property. Studies have pointed out that MnOx/WO3/TiO2 denitration catalyst can carry out NOx removing in a lower temperature by adjusting the content of tungsten trioxide and reaction environment, which is a good low-temperature denitration technology.
 
The steps of one-step-impregnation method to prepare MnOx/WO3/TiO2 denitration catalyst are like bellows:
1. Prepare titanium dioxide for further using;
2. Dissolve an amount of ammonium tungstate solution into the oxalic acid, then add a certain amount of manganese acetate, and add the carrier--titania under stirring to obtain a mixed solution;
3. Stir the mixed solution uniformly obtained in step 2 at 35℃ for 2 hours, and then immersed with stirring by heating to 85℃ for 4 hours, then dried at 110℃ for 12 hours;
4. Transfer the powder into a muffle furnace after ground to calcine at 450℃ for 3 hours, to generate the needed MnOx/WO3/TiO2 denitration catalyst.
 
Experimental results show that the temperature window of this catalyst reaches 80~240℃, thus to greatly reduce the reaction temperature; at the same time, appropriate tungsten trioxide added can significantly improve the catalytic activity, but too much or too little can cause activity decreases, and the excess tungsten trioxide will even reduce the low-temperature activity, but instead increase the activity of MnOx supported catalyst; in addition, the presence of oxygen will promote the oxidation of NO, and protect of the catalyst surface oxidation activity center at low temperatures, thus to facilitate ammonia absorption and activation.

 

WO3 SCR Denitration Catalyst Facing Technical Difficulty--Low Temperature Denitration

low temperature catalystTungsten trioxide SCR denitration catalyst will take more than 1/3 of the whole cost in the SCR denitration system. Currently, the technology has been widely used in the thermal power industry, 95% of the production line using SCR denitration technology in China, while there are successfully applications in the glass furnace and other industrial furnaces.
 
Tungsten trioxide SCR denitration catalyst can still have a good denitration effect, even at high nitrogen oxide emissions in power industry, so to achieve the emissions requirements. Ideally, the denitration rate SCR technology can enable the state of more than 90%, besides, the ammonia injected will almost completely react with nitrogen oxide makes it the best treatment technology for stationary sources denitration currently.
 
However, the fact is, SCR denitration, as the highly efficient technology is rarely applied in the cement industry. Why is this? Research indicates the unfavorable factors such as complex environmental conditions and higher investment at one-time limit the application. Its cost limitations performance as these, equipment increased means taking more space, large investment and higher operating costs.
 
The honeycomb tungsten trioxide SCR denitration catalyst is the most commonly used, which is taking the porous titanium dioxide as carrier, vanadium pentoxide and tungsten trioxide as the main active ingredients, with the optimum reaction temperature about 300℃~400 ℃. In the new industrial production, the temperature of exhaust emissions have been dropped to below 300℃; while, for implementing the national policy of saving energy and decreasing consuming, production lines more than 2500t/d are installing waste heat boiler, thus the exhaust gas temperature is about 150 ℃, all these above have presented new challenges to denitration catalyst. Thus, low-temperature denitration has become technical difficulty of tungsten trioxide SCR denitration catalyst.

 

Tungsten Copper Sintering Technologies Comparison (2/2)

In order to improve mixed-pressing, relevant scholars uses activated agent (Ni, Pd and other activated elements) to increase the solubility of W in liquid phase, which is beneficial for the sintering process. However the additives have a bad influence on the electrical and thermal conductivity of tungsten copper products. Pressure sintering is a kind of secondary processing after sintering, especially for the conditions that one-step forming can not meet the requirements. Although hot pressing, repressing and re-sintering and HIP (Hot Isostatic Pressing) can remarkably improve the properties of tungsten copper composite material, they are limited by the costs and the efficiency. In addition, using hammering or cold rolling of tungsten-copper composite material for secondary processing can greatly increase the density and mechanical properties of the material. But when the content of W is higher, the ductility of tungsten copper will decrease and the difficulty of machining will increase.

Spark Plasma Sintering (SPS), which is also known as Plasma Activated Sintering (PAS) or Field Assisted Sintering Technology (FAST). According to different powder media, SPS can be divided into conductive and non-conductive, there is a big difference in mechanism between them. Generally, conductive SPS will produce a large amount of Joule heat generated by DC pulse current graphite mold; and the current through the powder will induce electric discharge between powder particles and arouse plasma. With the increasing density of plasma, High-speed reverse movement of the particle surface of the particles have a greater impact, so that the gas adsorption of escape or break an oxide film, so that the surface to be purified and activated, will be conducive to sintering. However, instantaneous high temperature generated by the discharge causes evaporation and melting of the grain surface, the grain at the point of contact to form sintered neck.

tungsten copper SPS sintering technology

 

Recover Vanadium from WO3 SCR Denitration Catalyst

Vanadium, symbol V, a silvery white metal, has a very high melting point, which makes it a refractory metal together with niobium, tantalum, tungsten, molybdenum. As an active component, vanadium pentoxide is used in tungsten trioxide SCR denitration catalyst, and tungsten trioxide is exhibiting the role of anti-sulfide, anti-toxic. The toxicity of metal vanadium is very low, but its compounds (vanadium salts) are toxic to humans and animals, especially vanadium pentoxide has a very high toxic and can cause respiratory and nervous system, gastrointestinal, skin changed. So, in order to prevent environmental pollution, human poisoned, and also resource get recycled, the recovery of vanadium from waste SCR denitration catalyst is extremely necessary.

various valence states of vanadium
 
Studies have demonstrated a new method for recycling vanadium from tungsten trioxide SCR denitration catalyst, follow these steps:
1. Crushed the waste W-Ti-V based to 200-300 mesh;
2. Take electrolytic cell, and added an amount of anti-reducing strong electrolyte solution; then put the crushed catalyst into the cell, carry out constant current density electrolysis by controlling the current density, or constant pressure electrolysis by controlling the voltage;
3. Carrying out filtration to separate the solid and liquid, to obtain a mixed solution containing with vanadium;
4. Take out a new cell and take out the secondary electrolysis at the same condition;
5.Add alkaline solution into the mixture in the cathode, then add ammonium salt solution and stay overnight for precipitating vanadium, calcining the white solid obtained by filtration to get the yellow solid containing vanadium, thus to achieve the purpose of recycling vanadium.
 
This process of vanadium recovery can be operated at room temperature with a mild reaction condition, the electrolysis reaction has good chemical reaction selectivity, and vanadium can be almost completely recovered.

 

Tungsten Copper Sintering Technologies Comparison (1/2)

There are many kinds of tungsten copper sintering technologies, such as conventional infiltration, mixed-pressing, pressure sintering and new SPS (Spark Plasma Sintering), etc, which have their own advantages and disadvantages. Next, we analyze these different sintering technologies by the principle and the applications. First of all, infiltration, which is called melt immersion, is the most widely used in tungsten copper products currently. It is obtained by adding a small amount of tungsten powder or copper powder compacts made of tungsten powder and tungsten and copper infiltrated compacts stacked together, and thereafter sintered at a temperature above the melting point of copper and under reducing atmosphere or vacuum.

In the process of sintering, copper in a molten state to rely on capillary action infiltrated tungsten skeleton, two sintering and infiltration step can also be performed separately. Infiltration has many advantages, such as high density, excellent sintering properties and electrical and thermal conductivity, good arc ablation resistance. But liquid copper barely rely on capillary forces infiltrated tungsten skeleton, this will lead to coarse and uneven distribution of copper particles sintered tungsten particles at high temperatures easily grew up together. In addition, after infiltration machined to remove excess copper and will increase costs and reduce the yield.

Mixed - pressing sintering process is one of the most conventional powder metallurgy, which basic process is preparation →ball milling → compacting →sintering. Sintering can be also divided into two parts, one is solid phase sintering (temperature lower than the melting point of Cu), the other is liquid phase sintering (temperature higher than the melting point of Cu). Since the solid solubility in the liquid phase W Cu is small, the material can not be conveyed by dissolution and precipitation particles rounded manner, and tungsten and copper infiltration is poor, it is difficult to achieve densification.

 

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