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.

 

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 (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

 

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.

Tungsten Alloy Shielding For Radiation Pasteurization

Tungsten alloy shielding for radiation pasteurization is used for shielding the radiation released from the process of radiation pasteurization. Radiation pasteurization is a technology that uses ionizing radiation to kill the causative agent (including virus) to achieve the purpose of toxicity elimination. Its radioactive source is Co60 radioactive source which can release γ rays from a decay. The pests and bacteria hided in the fruits and vegetables would suffer from the physiological function changes and lost the ability to grow and develop after being exposed to these γ rays. So far, radiation pasteurization is widely used for the disinfection of various kinds of medical apparatus and instruments, such as catheters, cannulas, bandages, dressings, suture materials, surgical instruments, injection equipments, blood transfusion equipments, artificial kidney dialyzer, biological tissues for transplantation. It also can be used in pharmaceutical, food, agricultural products and customs, etc.

Co60 is a radioactive isotope of cobalt with a half-life of 5.27 years. Co60 decays by beta decay to the isotope nickel-60. The tungsten alloy shielding for radiation pasteurizationactivated nickel nucleus emits two gamma rays with energies of 1.17 and 1.33 MeV. After entering a living mammal, some of the Co60 are taken up by tissues, mainly the liver, kidneys, and bones, where the prolonged exposure to gamma radiation can cause cancer. Low levels of gamma rays cause a stochastic health risk, which for radiation dose assessment is defined as the probability of cancer induction and genetic damage. High doses produce deterministic effects, which is the severity of acute tissue damage that is certain to happen.

Tungsten alloy shielding for radiation pasteurization is mainly used for shielding the β and γ radiation  released from the process of radiation pasteurization. Tungsten alloy shielding mainly uses high gravity alloy which has the characteristics of high density and innocuity. Therefore tungsten alloy shielding for radiation pasteurization has excellent shielding performance to shield  the β and γ radiation  generated during the process of radiation pasteurization, to avoid resulting in radiation damage. In addition, tungsten alloy shielding for radiation pasteurization is more environmentally friendly than some traditional shielding materials, such as lead, and will not pollute the environment. 

 

Tungsten Alloy Nuclear Radiation Detector

tungsten alloy nuclear radiation detectorTungsten alloy nuclear radiation detector, also known as tungsten alloy detecting element, is used to detect nuclear radiation and its properties(including the types, strength ,the energy and nuclear lifetime of nuclear radiation) by utilizing radiation rays to interact with substances to induce a series of effects(such as luminescence phenomenon, ionization effect, physical and chemical changes).It usually made up of a detector, a display unit, a measuring element and a power source, and mainly includes semiconductor detector, gas ionization detector and scintillation detector. Tungsten alloy nuclear radiation detector is widely used in public places, laboratories, quarries, metal processing plants, oil fields and oil pipeline equipment and other departments, for inspection of the radioactivity of underground drill pipe and equipment and building materials, local radiation leakage and contamination and landfill and garbage dump which has the risk of nuclear radiation.

Nuclear radiation, also known as ionization radiation, is a microscopic particle released from the process of a nucleus changes from a structure (or an energy state) to another kind of structure (or another energy state) to cause ionization or excitation material. The types of nuclear radiation include gamma rays, α rays and βrays. Gamma ray is extremely high-frequency electromagnetic radiation and thus consists of high-energy photons. It is penetrating, and can lead to damage at a cellular level, resulting in diffuse damage throughout the body;α rays are generally produced in the process ofα decay. It can enter the body to destroy the human tissues by being inhaled, ingested or injected, αradiation is the most destructive form of ionizing radiation; β rays are able to penetrate living tissues to a certain extent and can change the structure of struck molecules(such as DNA molecules). In most cases, such change can be considered to be damage, with results possibly as severe as cancer or death.

Tungsten alloy nuclear radiation detector uses the tungsten alloy material with high density. Because the radiation shielding capability of a metal material increases with the increasing of its density, so the tungsten alloy nuclear radiation detector has excellent radiation shielding capability. When using a tungsten alloy nuclear radiation detector, the tungsten alloy can absorb and shield the nuclear radiation in a high degree to avoid them doing harm to human body while reaching the goal of nuclear radiation detection.

 

Tungsten Alloy γ-Ray Level Gage

tungsten alloy γ-ray level gageTungsten alloy γ-ray level gage, also known as tungsten alloy γ-ray content gauge or tungsten alloy γ-ray material level meter, is a measuring instrument for mass level by using its characteristic of the strength of rays suffered by detector is various from the levels. It is also an isotope material level meter. Tungsten alloy γ-ray level gage mainly consists of radiation source, detector and transducer. Generally, the radiation source is Co60 or Cs137 radioactive source contained by tungsten alloy container. The function of detector is to detect the rays, and then change the light signals produced by it into electrical signals. While the electrical signals are transformed into contact signals or standard current signals and output to the DOS and other peripheral equipments by transducer. At present, many advanced tungsten alloy γ-ray level gage collectively call detector and transducer as detector.

Tungsten alloy γ-ray level gage has the characteristic of easy operation, simple structure and high measurement accuracy, is particularly useful for measurement of stuff level in harsh conditions(including high pressure, high temperature, high viscosity, high corrosivity, high toxicity and smoke concentration, boiling conditions)or in complicated conditions where general instruments can't or is difficult to use, or for liquid level measurement in the high pressure container which exists liquid drop and liquid surface fluctuation. The material to be measured can be powder, granular solid or liquid. Tungsten alloy γ-ray level gage is mainly used in papermaking, petrochemical engineering, coal industry, mining, steel, thermal power industry, etc. It is only applies to the measurement of two-phase interface.

Due to theγ rays released from theγ-ray level gage can cause DNA and cellular damage, chromosome aberration, chronic and acute radiation sickness, cancer induced. Theγ-ray level gage usually is tungsten alloy γ-ray level gage whose radiation source container is tungsten alloy container. Tungsten alloy γ-ray level gage has high density and great radiation shielding performance, which make it absorb and shield γ rays in a high degree, reducing the harm on human body, to protect the human from the radiation. Moreover, it is environmentally friendly.  

 

Typical Recovery Process of Waste WO3 Cellular SCR Denitration Catalyst

Theoretically, SCR denitration catalyst has unlimited life, but it’s life limited by various reasons; at the same time, under the collective effect of the economy and market, the catalyst has shorter and shorter life, and a large amount of waste tungsten trioxide denitration catalysts are produced. For the continually produced waste catalysts, the best way to treat is resources renewable (the regeneration frequency can only reach 2~3 times); followed by is recycling to ensure maximum utilization of resources, thus realize the goal of saving resources, protecting the environment; and the worst treatment way is landfill with harmless.

cellular SCR denitration catalyst
 
The steps of typical recovery processing of waste honeycomb SCR catalyst are as follows:
1. SCR spent catalyst was carried out pretreatment like washing, removing ash, then wet grinding, leaching under high temperature and pressure;
2. Adding hydrochloric acid into the leach solution to adjust pH value and remove impurities;
3. Adding hydrochloric acid into leach residue, calcining after fully react to prepare titanium dioxide or titanium-rich material;
4. Preparation of ammonium paratungstate;
5. Preparation of vanadium pentoxide;
6. wastewater reuse treatment.
 
The main products of this process have properties like high purity and recovery rate, mainly as follows: the content of titanium dioxide in rutile titanium dioxide is up to about 90%, and the recovery rate of titanium dioxide is nearly 90%; the content of tungsten trioxide in ammonium paratungstate can be higher than 99%, the recovery rate of tungsten oxide maybe higher than 80%; the content of vanadium pentoxide can reach to 93%, and the recovery rate is higher than 60%.
 
Also the compound with Na and Cl elements introduced can get recycled, the recycling cost of raw material can be lower.
 
In addition, there is no emission of secondary pollutants, mainly performance as follows: the using of washing ash with high-pressure-water and the washed water reused; crushing, fine grinding and leaching when the material is wet; the side-products can be directly sold; wastewater spray for absorbing calcination exhaust.

 

WO3 SCR Waste Denitration Catalyst Recovery Process

There are four processes for recycling waste tungsten trioxide SCR denitration catalyst as following:
1. The waste tungsten trioxide SCR denitration catalyst was crushed and re-added to the new manufacturing process of catalyst. In this process, the amount of recovery catalyst is limited, thus the goal of recycling all the waste catalyst can’t be realized.
2. The material carried out sodium treatment and roasting→precipitate V by ammonium chloride from the leachate→ precipitate tungsten by calcium chloride→ de-integrating the Na4TiO4 by sulfuric acid; or sodium treatment and roasting→ precipitate tungsten by calcium chloride→ realize the separation of tungsten and V by forming ammonium paratungstate.
Such technology has the following properties:
(1) The material should be crushed before roasting, and always require the particle size equals to or less than 200μm, otherwise it will cause a serious loss of fly ash and large amounts of carbon dioxide emissions in the calcination process;
(2) The heat cannot get fully used;
(3)The separation step and impurity removal method of waste tungsten trioxide denitration catalyst isn’t well considered, and cause the purity of recovered products limited;
(4) does not form a good cycle of process wastewater reuse.

steel SCR denitration catalyst

3. Two times of electrolysis with strong electrolyte solution→ adjust pH with ammonium to precipitate vanadium. The industrial application and energy consumption of this process is unknown; besides, W, Ti and other components cannot be separated for recycling.
4. The pretreatment of removing ash→ alkaline leaching at high temperature and pressure→ removing impurities with magnesium salts→ precipitate tungsten and vanadium with calcium salts→ de-integrating the tungsten, vanadium and calcium salts→ extract vanadium→ prepare the material which is rich in titanium→ wastewater reuse treatment. This is the better treatment processing with purity of the recovered products well controlled; moreover, elements Na and Cl well recycling and the energy get fully used.

 

 

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