Selective catalyticreduction of NO x using ammonia as the reducing agent was patented in the United States by the Engelhard Corporation in 1957. Development of SCR technology continued in Japan and the US in the early 1960s with research focusing on less expensive and more durable catalyst agents. The first large-scale SCR was installed by the IHI Corporation in 1978.[1]
SCR systems are now the preferred method for meeting Tier 4 Final and EURO 6 diesel emissions standards for heavy trucks, and also for cars and light commercial vehicles. As a result, emissions of NOx, particulates, and hydrocarbons have been reduced by as much as 95% when compared with pre-emissions engines.[2]
Chemistry
The NO x reduction reaction takes place as the gases pass through the catalyst chamber. Before entering the catalyst chamber, ammonia, or other reductant (such as urea), is injected and mixed with the gases. The chemical equation for a stoichiometric reaction using either anhydrous or aqueous ammonia for a selective catalytic reduction process is:
With several secondary reactions:
With urea, the reactions are:
As with ammonia, several secondary reactions also occur in the presence of sulfur:
The ideal reaction has an optimal temperature range between 630 and 720K (357 and 447°C), but can operate as low as 500K (227°C) with longer residence times. The minimum effective temperature depends on the various fuels, gas constituents, and catalyst geometry. Other possible reductants include cyanuric acid and ammonium sulfate.[3]
Base metal catalysts, such as vanadium and tungsten, lack high thermal durability, but are less expensive and operate very well at the temperature ranges most commonly applied in industrial and utility boiler applications. Thermal durability is particularly important for automotive SCR applications that incorporate the use of a diesel particulate filter with forced regeneration. They also have a high catalysing potential to oxidize SO 2 into SO 3, which can be extremely damaging due to its acidic properties.[5]
Zeolite catalysts have the potential to operate at substantially higher temperature than base metal catalysts; they can withstand prolonged operation at temperatures of 900K (627 °C) and transient conditions of up to 1120K (847 °C). Zeolites also have a lower potential for SO 2 oxidation and thus decrease the related corrosion risks.[5]
Iron- and copper-exchanged zeolite urea SCRs have been developed with approximately equal performance to that of vanadium-urea SCRs if the fraction of the NO 2 is 20% to 50% of the total NO x.[6] The two most common catalyst geometries used today are honeycomb catalysts and plate catalysts. The honeycomb form usually consists of an extruded ceramic applied homogeneously throughout the carrier or coated on the substrate. Like the various types of catalysts, their configuration also has advantages and disadvantages. Plate-type catalysts have lower pressure drops and are less susceptible to plugging and fouling than the honeycomb types, but are much larger and more expensive. Honeycomb configurations are smaller than plate types, but have higher pressure drops and plug much more easily. A third type is corrugated, comprising only about 10% of the market in power plant applications.[1]
Reductants
Several nitrogen-bearing reductants are currently used in SCR applications including anhydrous ammonia, aqueous ammonia or dissolved urea. All those three reductants are widely available in large quantities.
Anhydrous ammonia can be stored as a liquid at approximately 10 bar in steel tanks. It is classified as an inhalation hazard, but it can be safely stored and handled if well-developed codes and standards are followed. Its advantage is that it needs no further conversion to operate within a SCR and is typically favoured by large industrial SCR operators. Aqueous ammonia must be first vaporized in order to be used, but it is substantially safer to store and transport than anhydrous ammonia. Urea is the safest to store, but requires conversion to ammonia through thermal decomposition. [7] At the end of the process, the purified exhaust gasses are sent to the boiler or condenser or other equipment, or discharged into the atmosphere.[8][1]
Limitations
Most catalysts are given a finite service life due to known amounts of contaminants in the untreated gas. The most notable complication is the formation of ammonium sulfate and ammonium bisulfate from sulfur and sulfur compounds when high-sulfur fuels are used, as well as the undesirable catalyst-induced oxidation of SO 2 to SO 3 and H 2SO 4. In applications that use exhaust gas boilers, ammonium sulfate and ammonium bisulfate can accumulate on the boiler tubes, reducing steam output and increasing exhaust back-pressure. In marine applications, this can increase fresh water requirements as the boiler must be continuously washed to remove the deposits.
Most catalysts on the market have porous structures and a geometries optimized for increasing their specific surface area (a clay planting pot is a good example of what SCR catalyst feels like). This porosity is what gives the catalyst the high surface area needed for reduction of NOx. However, soot, ammonium sulfate, ammonium bisulfate, silica compounds, and other fine particulates can easily clog the pores. Ultrasonic horns and soot blowers can remove most of these contaminants while the unit is online. The unit can also be cleaned by being washed with water or by raising the exhaust temperature.
Of more concern to SCR performance are poisons, which will chemically degrade the catalyst itself or block the catalyst's active sites and render it ineffective at NO x reduction, and in severe cases this can result in the ammonia or urea being oxidized and a subsequent increase in NO x emissions. These poisons are alkali metals, alkaline earth metals, halogens, phosphorus, sulfur, arsenic, antimony, chromium, heavy metals (copper, cadmium, mercury, thallium, and lead), and many heavy metal compounds (e.g. oxides and halides).
Most SCRs require tuning to properly perform. Part of tuning involves ensuring a proper distribution of ammonia in the gas stream and uniform gas velocity through the catalyst. Without tuning, SCRs can exhibit inefficient NOx reduction along with excessive ammonia slip due to not utilizing the catalyst surface area effectively. Another facet of tuning involves determining the proper ammonia flow for all process conditions. Ammonia flow is in general controlled based on NOx measurements taken from the gas stream or preexisting performance curves from an engine manufacturer (in the case of gas turbines and reciprocating engines). Typically, all future operating conditions must be known beforehand to properly design and tune an SCR system.
Ammonia slip is an industry term for ammonia passing through the SCR unreacted. This occurs when ammonia is injected in excess, temperatures are too low for ammonia to react, or the catalyst has been poisoned. In applications using both SCR and an alkaline scrubber, the use of high-sulfur fuels also tend to significantly increase ammonia slip, since compounds such as NaOH and Ca(OH)2 will reduce ammonium sulfate and ammonium bisulfate back into ammonia:
Temperature is SCR's largest limitation. Engines all have a period during start-up where exhaust temperatures are too low, and the catalyst must be pre-heated for the desired NOx reduction to occur when an engine is first started, especially in cold climates.
Power plants
In power stations, the same basic technology is employed for removal of NO x from the flue gas of boilers used in power generation and industry. In general, the SCR unit is located between the furnaceeconomizer and the air heater, and the ammonia is injected into the catalyst chamber through an ammonia injection grid. As in other SCR applications, the temperature of operation is critical. Ammonia slip (unreacted ammonia) is also an issue with SCR technology used in power plants.
A significant operational difficulty in coal-fired boilers is the binding of the catalyst by fly ash from the fuel combustion. This requires the usage of sootblowers, ultrasonic horns, and careful design of the ductwork and catalyst materials to avoid plugging by the fly ash. SCR catalysts have a typical operational lifetime of about 16,000 – 40,000 hours (1.8 – 4.5 years) in coal-fired power plants, depending on the flue gas composition, and up to 80,000 hours (9 years) in cleaner gas-fired power plants.
Poisons, sulfur compounds, and fly ash can all be removed by installing scrubbers before the SCR system to increase the life of the catalyst, though in most power plants and marine engines, scrubbers are installed after the system to maximize the SCR system's effectiveness.
In 2007, the United States Environmental Protection Agency (EPA) enacted requirements to significantly reduce harmful exhaust emissions. To achieve this standard, Cummins and other diesel engine manufacturers developed an aftertreatment system that includes the use of a diesel particulate filter (DPF). As the DPF does not function with low-sulfur diesel fuel, diesel engines that conform to 2007 EPA emissions standards require ultra-low sulfur diesel fuel (ULSD) to prevent damage to the DPF. After a brief transition period, ULSD fuel became common at fuel pumps in the United States and Canada. The 2007 EPA regulations were meant to be an interim solution to allow manufacturers time to prepare for the more stringent 2010 EPA regulations, which reduced NOx levels even further.[10]
2010 EPA regulations
Hino truck and its Standardized SCR Unit which combines SCR with Diesel Particulate Active Reduction (DPR). DPR is a diesel particulate filtration system with regeneration process that uses late fuel injection to control exhaust temperature to burn off soot.
Diesel engines manufactured after January 1, 2010 are required to meet lowered NOx standards for the US market.
All of the heavy-duty engine (Class 7-8 trucks) manufacturers except for Navistar International and Caterpillar continuing to manufacture engines after this date have chosen to use SCR. This includes Detroit Diesel (DD13, DD15, and DD16 models), Cummins (ISX, ISL9, and ISB6.7), Paccar, and Volvo/Mack. These engines require the periodic addition of diesel exhaust fluid (DEF, a urea solution) to enable the process. DEF is available in bottles and jugs from most truck stops, and a more recent development is bulk DEF dispensers near diesel fuel pumps. Caterpillar and Navistar had initially chosen to use enhanced exhaust gas recirculation (EEGR) to comply with the Environmental Protection Agency (EPA) standards, but in July 2012 Navistar announced it would be pursuing SCR technology for its engines, except on the MaxxForce 15 which was to be discontinued. Caterpillar ultimately withdrew from the on-highway engine market prior to implementation of these requirements.[13]
Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the formula NH3. A stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous waste, and it contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to fertilisers. Around 70% of ammonia produced industrially is used to make fertilisers in various forms and composition, such as urea and diammonium phosphate. Ammonia in pure form is also applied directly into the soil.
In chemistry, amines are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as monochloramine.
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combustion does not always result in fire, because a flame is only visible when substances undergoing combustion vaporize, but when it does, a flame is a characteristic indicator of the reaction. While activation energy must be supplied to initiate combustion, the heat from a flame may provide enough energy to make the reaction self-sustaining.
The Haber process, also called the Haber–Bosch process, is the main industrial procedure for the production of ammonia. The German chemists Fritz Haber and Carl Bosch developed it in the first decade of the 20th century. The process converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction with hydrogen (H2) using an iron metal catalyst under high temperatures and pressures. This reaction is slightly exothermic (i.e. it releases energy), meaning that the reaction is favoured at lower temperatures and higher pressures. It decreases entropy, complicating the process. Hydrogen is produced via steam reforming, followed by an iterative closed cycle to react hydrogen with nitrogen to produce ammonia.
The Ostwald process is a chemical process used for making nitric acid (HNO3). Wilhelm Ostwald developed the process, and he patented it in 1902. The Ostwald process is a mainstay of the modern chemical industry, and it provides the main raw material for the most common type of fertilizer production. Historically and practically, the Ostwald process is closely associated with the Haber process, which provides the requisite raw material, ammonia (NH3).
Urea, also called carbamide, is an organic compound with chemical formula CO(NH2)2. This amide has two amino groups joined by a carbonyl functional group. It is thus the simplest amide of carbamic acid.
In chemistry, there are three definitions in common use of the word "base": Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century.
A catalytic converter is an exhaust emission control device which converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalyzing a redox reaction. Catalytic converters are usually used with internal combustion engines fueled by gasoline or diesel, including lean-burn engines, and sometimes on kerosene heaters and stoves.
Ammonium bicarbonate is an inorganic compound with formula (NH4)HCO3. The compound has many names, reflecting its long history. Chemically speaking, it is the bicarbonate salt of the ammonium ion. It is a colourless solid that degrades readily to carbon dioxide, water and ammonia.
Ammonium carbonate is a salt with the chemical formula (NH4)2CO3. Since it readily degrades to gaseous ammonia and carbon dioxide upon heating, it is used as a leavening agent and also as smelling salt. It is also known as baker's ammonia and is a predecessor to the more modern leavening agents baking soda and baking powder. It is a component of what was formerly known as sal volatile and salt of hartshorn, and produces a pungent smell when baked. It comes in the form of a white powder or block, with a molar mass of 96.09 g/mol and a density of 1.50 g/cm3. It is a strong electrolyte.
In chemistry, a trimer is a molecule or polyatomic anion formed by combination or association of three molecules or ions of the same substance. In technical jargon, a trimer is a kind of oligomer derived from three identical precursors often in competition with polymerization.
A nitrogen oxide sensor or NOx sensor is typically a high-temperature device built to detect nitrogen oxides in combustion environments such as an automobile, truck tailpipe or smokestack.
Diesel exhaust fluid is a liquid used to reduce the amount of air pollution created by a diesel engine. Specifically, DEF is an aqueous urea solution made with 32.5% urea and 67.5% deionized water. DEF is consumed in a selective catalytic reduction (SCR) that lowers the concentration of nitrogen oxides in the diesel exhaust emissions from a diesel engine.
In atmospheric chemistry, NOx is shorthand for nitric oxide and nitrogen dioxide, the nitrogen oxides that are most relevant for air pollution. These gases contribute to the formation of smog and acid rain, as well as affecting tropospheric ozone.
Hydrodesulfurization (HDS), also called hydrotreatment or hydrotreating, is a catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products, such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of removing the sulfur, and creating products such as ultra-low-sulfur diesel, is to reduce the sulfur dioxide emissions that result from using those fuels in automotive vehicles, aircraft, railroad locomotives, ships, gas or oil burning power plants, residential and industrial furnaces, and other forms of fuel combustion.
BlueTEC is Mercedes-Benz Group's marketing name for engines equipped with advanced NOx reducing technology for vehicle emissions control in diesel-powered vehicles. The technology in BlueTec vehicles includes a selective catalytic reduction (SCR) system that uses diesel exhaust fluid, and a system of NOx adsorbers the automaker calls DeNOx, which uses an oxidizing catalytic converter and diesel particulate filter combined with other NOx reducing systems.
Selective non-catalytic reduction (SNCR) is a method to lessen nitrogen oxide emissions in conventional power plants that burn biomass, waste and coal. The process involves injecting either ammonia or urea into the firebox of the boiler at a location where the flue gas is between 1,400 and 2,000 °F (760 and 1,090 °C) to react with the nitrogen oxides formed in the combustion process. The resulting product of the chemical redox reaction is molecular nitrogen (N2), carbon dioxide (CO2), and water (H2O).
Ammonium carbamate is a chemical compound with the formula [NH4][H2NCO2] consisting of ammonium cation NH+4 and carbamate anion NH2COO−. It is a white solid that is extremely soluble in water, less so in alcohol. Ammonium carbamate can be formed by the reaction of ammonia NH3 with carbon dioxide CO2, and will slowly decompose to those gases at ordinary temperatures and pressures. It is an intermediate in the industrial synthesis of urea (NH2)2CO, an important fertilizer.
Dan Luss is an American chemical engineer, who is the Cullen Professor of Chemical Engineering at the University of Houston. He is known for his work in chemical reaction engineering, complex reacting systems, multiple steady-states reactor design, dynamics of chemical reactors, and combustion.
Ammonia pollution is pollution by the chemical ammonia (NH3) – a compound of nitrogen and hydrogen which is a byproduct of agriculture and industry. Common forms include air pollution by the ammonia gas emitted by rotting agricultural slurry and fertilizer factories while natural sources include the burning coal mines of Jharia, the caustic Lake Natron and the guano of seabird colonies. Gaseous ammonia reacts with other pollutants in the air to form fine particles of ammonium salts, which affect human breathing. Ammonia gas can also affect the chemistry of the soil on which it settles and will, for example, degrade the conditions required by the sphagnum moss and heathers of peatland.
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