Selective Non-Catalytic Reduction

SNCR reduces NOx into molecular nitrogen (N2) and water (H2O). The reagent is in-jected into the flue gas after the combustion. The target temperature for the rea-gents is 850-1300 ℃. The reaction is selective, since it needs a specific temperature and oxygen to work. The reagent is injected thought nozzles, which are located usu-ally into two zones, each zone covers one layer. Two reagents are used: ammonia (NH3) and urea [CO(NH2)2], both are ammonia-based. “Reactants are substances ini-tially present in a chemical reaction that are consumed during the reaction to make products.” Both reagents first vaporize in the boiler and then decomposes, into free radicals (NH3; NH2). With proper mixing, these radicals are in contact with the nitro-gen oxides, reducing the NOx into N2. The reductions reaction for ammonia is as fol-lows:

2𝑁𝑂 + 2𝑁𝐻₃ +¹₂𝑂₂ → 2𝑁₂+ 3𝐻₂𝑂 (6)

Reaction for urea is as follows:

2𝑁𝑂 + 𝐶𝑂(𝑁𝐻₂)₂+¹₂𝑂₂ → 2𝑁₂+ 𝐶𝑂₂+ 𝐻₂𝑂 (7)

Both reactions (6,7) can form nitrous oxide (N2O), as a by-product. However, with the urea the formation is more prevalent, which can be up to 30% of the products. Ni-trous oxide is a greenhouse gas.

Main costs from the SNCR-system comes from the reagents, which are used. Urea is more expensive than ammonia. The reagents have different properties; thus, the re-agents need different storing conditions. Typical properties of the reagent are shown in the Table 4.

Table 4. Properties of Urea and Ammonia. (Sorrels, John L. 2015, adapted)

Property Urea Solution Aqueous Ammonia

Chemical formula CO(NH₂)₂ NH₃

Molecular Weight of reagent 60,06 17,03

Liquid or gas at normal air temperature

Crystallization temperature 18°C –78°C

Flammability limits in air Non-flammable Lower explosion limit = 16%

NH₃ by volume Upper explosion limit = 25%

NH₃ by volume Threshold limit value (health

effects)

Not specified 25ppm

Odor Slight (ammonia-like) Pungent odor @ 5ppm or

more Acceptable materials for

stor-age Plastic, steel, or stainless

steel (no copper or copper-based alloys or zinc/alumi-num fitting)

Steel tank, capable of handling at least 172 Kpa pressure (no copper or copper-based alloys, etc)

Ammonia can be used in anhydrous or aqueous form, and it requires permits when stored greater than 28% concentrations by weight. The aqueous form (NH4OH) is usually preferred since the easier storing conditions. However, this requires more space and causes increase in the transportation costs. The anhydrous ammonia re-quires a pressurized container as it a gas in normal pressure. The Urea has a low freezing point of 18 ℃ compared to the -78 ℃ of anhydrous ammonia (more proper-ties in Table 4). This causes problems with the storing and injection, since a heating system is usually required. The urea is stored in 50% aqueous form. In addition, the urea solution is usually more economical, since the transport costs are lower. The main benefit for urea over ammonia, is nontoxicity of the urea. Furthermore, the liq-uid form of urea is less volatile and storing the reagent is safer. Lastly the droplets can have better mixing since they push further into the flue gas stream.

3.3.3.1 SNRC design variables Reaction temperature

Reaction temperature needs to be considered, when placing the injection nozzles to the boiler. If the temperature is too low, reaction will be too slow and ammonia slip is possible. When the temperature is too high, reagents forms NOx via oxidization.

For the ammonia ideal temperature range is 870-1050 ℃ and for the urea 900-1150

℃. At excessive high temperatures ammonia decomposes into nitric oxide as follows:

4𝑁𝐻₃+ 5𝑂₂ → 4𝑁𝑂 + 6𝐻₂𝑂 (8)

Figure 9. Temperature effect on reduction efficiency (Sorrels, John L. 2015, adapted)

Residence time

Residence time represents how long the reactants are present in the reaction. With longer residence times, comes better efficiency for conversion. Low residence time, in high temperatures, or high residence time, in a controlled temperature (980 ℃) provides the highest reduction efficiency. Residence time depends on the boiler de-sign and overall residence time is not the most de-significant factor in NOx reduction.

The reagents have a different reaction paths when injected. When urea is injected the water from the mixture starts to evaporate, while it is mixing with the flue gases.

After water evaporation urea is decomposed into NH3 . Up next ammonia decom-poses into free radicals and NH2. Lastly free radicals react, and NOx reduction takes place in the flue gas. This causes longer residence times and allows urea to work in higher injection temperatures. Ammonia evaporates and decomposes while being heated by the flue gases. Furthermore, causing ammonia to react faster and in lower temperature range.

Degree of mixing and coverage

Degree of mixing and coverage needs to be sufficient. This is done by atomizer noz-zles, which are divided around the boiler. Usually for more than one level, depending on the boiler temperature ranges. The diameter of the droplet specifies the evapora-tion time and trajectory for the droplets. Large droplets survive further into the stream and the large droplets have a longer volatilization time, increasing the re-quired residence time. The modifications that will have an impact on the NOx reduc-tion are as follows: pressure (energy of the droplets), boiler level coverage (number of injectors), increase in injection levels, different nozzle designs (particle size, spray, angle, direction). Ammonia needs to be distributed sufficiently, due to its volatile na-ture.

Uncontrolled NOx

NOx concentration affects to the reaction rate of the reduction process. The lower the concentration, lower the efficiency of the reduction. Lower concentrations of NOx also need a lower temperature to convert. Thermodynamic factors are limiting the conversion in low NOx concentrations.

Normalized Stoichiometric Ratio

Normalized Stoichiometric Ratio (NSR) shows how much reagent is needed for each mole of NOx. Usually the NSR is 0,5 to 3moles of ammonia for each mole of NOx. The ratio is determined by boiler characteristics. In addition, the ratio can be decreased if degree of mixing, residence time and temperature ranges are optimal.

Ammonia slip

Ammonia slip is excess reagent in the flue gas stream. Desired NOx reduction always has ammonia slip, due to flue gases cannot be mixed well enough, to gain the perfect NSR. The unreacted ammonia is carried out into the atmosphere and where it causes several, health related issues through the air. Ammonia creates ammonium-bisulfate (NH4)HSO4 and ammonium sulfate (NH4)2HSO4. This can cause corrosion in the boiler, ducts and fans. (Richardson, Lee 1999; CATC 1999; Sorrels, John L. 2015)