AM-02-27 FCC FLUE GAS EMISSION CONTROL OPTIONS

Authors: Phillip K. Niccum Chief Technology Engineer, FCC Eusebius Gbordzoe Principal Engineer, FCC Stephan Lang Principal Engineer, Environmental Publication / Presented: NPRA 2002 Annual Meeting Date: March 17-19, 2002 Notes: Marriott Rivercenter Hotel San Antonio, TX

Introduction
Fluid Catalytic Cracking (FCC) is widely used to produce products such as gasoline and C3/C4 olefins from lower value, higher molecular weight, petroleum fractions. As oil refining has evolved over the last 60 years, the FCC process has evolved with it, meeting the challenges of cracking heavier, more contaminated feedstocks, while still accommodating increasingly stringent environmental regulations. Combustion of coke in the FCC regenerator produces a variety of potential atmospheric pollutants, but these can be controlled at or below egulatory mandated levels using a variety of technologies as summarized in Figure 1. For many decades, carbon monoxide (CO) emissions from U.S. FCC operations have been effectively controlled to levels below 500 ppm by the use of CO boilers and complete CO combustion with CO combustion promoting catalyst
Figure 1: FCCU Flue Gas Emissions And Control Technologies
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are NOx emissions becoming a major issue for many FCC operators. No single flue gas emission control technology or combination of technologies is best for all applications. The optimum choice for a given refiner depends on a number of factors, such as regenerator operating mode, feedstock quality, targeted emission level.

Regulatory Review
In the United States, there are currently three major regulatory drivers impacting FCCU flue gas controls and thus future emission limitations. These are (1) the continuing application of New Source Performance Standards (NSPS), (2) the up-coming implementation of Hazardous Air Pollutant (HAP) controls via what is known as MACT II regulations, and (3) the U.S. Environmental Protection Agency (EPA) enforcement actions and their Consent Decrees. Each of these regulatory forces impacts the selection of future emission control technology when site-specifics are addressed and they need to be integrated into any master compliance planning effort. At the same time, FCC units operating outside of the U.S. are also under pressure to reduce emissions, sometimes to levels even lower than required in the U.S.

Carbon Monoxide Complete Combustion/CO Promoter CO Boiler (CO Incinerator) Particulates Third Stage Separation Electrostatic Precipitation Flue Gas Scrubbing Sulfur Oxides Feed Desulfurization Flue Gas Scrubbing SOx Catalyst Additives Nitrogen Oxides Selecive Catalytic Reduction Selective Non-Catalytic Reduction NOx Catalyst Additives Counter-Current Regeneration

NSPS
New Source Performance Standards for FCCUs are well established for the control of particulate matter, carbon monoxide, and sulfur dioxide emissions (1). These standards apply to FCC units constructed after January 17, 1984 as well as existing units that trigger their applicability with either of the following occurrences: Major FCC modifications (reconstruction) wherein cumulative investments over a two year period exceed 50 % of the fixed capital cost of facility replacement. This involves maintaining proper documentation on file for inspection (2). Changes in equipment or operation, which increase the rate to the atmosphere of any pollutant to which a standard applies. NSPS does not set explicit limits on NOx emissions from FCC regenerators. However, site and situation specific NOx limits may be established at the time the FCC unit is permitted or modified.

additives. (The FCC units built in the 1940s operated with flue gas CO emissions of approximately 10 vol% or 100,000 ppm!). Particulate emissions have also been controlled through the application of more attrition resistant catalyst and improved regenerator cyclone designs, as well as third stage separators and electrostatic precipitators downstream of the FCC regenerator. Technologies to control SOx emissions have also been widely applied, utilizing a combination of technologies (alone or in combination) such as feed desulfurization, flue gas scrubbing, and SOx reducing catalyst additives. NOx emissions from FCC regenerators has long been a topic of academic study and discussion but only now

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MACT II
When the Maximum Achievable Control Technology (MACT) standards were issued for petroleum refineries in August 1995(3), the EPA did not address flue gas from existing FCCUs, catalytic reformers, and sulfur recovery units. In September 1998, the EPA proposed National Emission Standards for Hazardous Air Pollutants (NESHAP) to cover these remaining three types of refining process units (4). This NESHAP, commonly referred to as MACT II regulations, will establish the allowable pollution levels for FCCU regenerator particulate matter and carbon monoxide emissions. As presently proposed, MACT II particulate matter and carbon monoxide limits will be the same as the current NSPS requirements but will apply to FCC units previously grandfathered with respect to NSPS. The MACT II regulatory proposal uses CO control to NSPS levels (500 ppmvd) as a surrogate to demonstrate complete combustion of all organic HAPs that might otherwise be defined. The MACT II regulatory proposal uses nickel as a surrogate for other metals HAPs found either in crude feedstocks or FCC catalyst formulations, and seeks to limit its emission through control of particulate matter emitted with flue gas to the atmosphere. Metal HAPs include compounds of antimony, arsenic, beryllium, cadmium, chromium, cobalt, lead, manganese, mercury, nickel and selenium. A direct alternative limit of 0.029 lb/hr of Ni from the FCC regenerator stack has also been proposed. Some operators with very low nickel feedstocks may choose to address this specific nickel limit rather than the PM limit for MACT II compliance. It has been estimated that about one half of the nearly 100 FCC units operating in the U.S. will require installation of pollution control technology to reduce particulate emissions to the levels required by MACT II.

projects may ultimately portend revisions to NSPS limits. The breakdown of how these regulations apply to FCC flue gas emissions is summarized in Table 1. Table 1 FCCU Emissions Control Regulatory Drivers
Pollutant Emissions/ Regulatory Item Particulate Matter Opacity Carbon Monoxide (CO) Sulfur Dioxide (SO2) Nickel Compounds (Ni) Nitrogen Oxides (NOx) Continuous Emissions Monitoring Record Keeping Applicability of Major Regulatory Drivers EPA Consent Decrees No No No Yes No Yes Yes Yes MACT II Yes for Ni No Yes No Yes via PM No Yes Yes NSPS Yes Yes Yes Yes Yes via MACT II No Yes Yes

The EPA Consent Decrees have involved schedules with interim compliance dates stretching to 2008 for each refiner. The MACT II final rule, originally scheduled to be issued on May 15, 1999, is now expected sometime in 2002(6) and will take effect 3 years after it is adopted. The NSPS covering FCCU regenerator flue gas is not currently under review and revisions are not expected until the current Consent Decrees with refiners are completed. Current emission limits applicable to FCCU regenerators are presented in Table 2. Table 2 FCCU Regenerator Flue Gas Emission Control Requirements In many parts of the world, particulate emission limits are expressed in units of milligrams per normal cubic meter of flue gas. Table 3 illustrates the approximate relationship between FCC flue gas particulate concentration in units of mg/Nm3 and the EPA limit of 1.0 lb particulate matter/1000 lb coke burned. The table shows that the particulate concentration corresponding to the MACT II limit is a function of the FCC regenerator operating mode and that the value will typically be between about 95 and 125 mg/Nm3.

EPA Consent Decrees

Most recently, the EPA has entered into binding Consent Decrees (5) with several major U.S. refiners to significantly reduce the amount of SO2 as well as NOx emissions from their FCC regenerators. Since the SO2 emission limitations sought are significantly lower than NSPS levels, their implementation on existing sources via these consent decree

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Pollutant Particulate Matter (PM)

Limit 1lb PM/ 1000 lb coke Burned

Reference 40 CFR 60.102(a)(1)

Comments Incremental 0.10 lb/million Btu (PM allowed from supplemental liquid or solid fuel red in incinerator or waste heat boiler per 40 CFR 60.102(b) CMES required under 60.105(a)(1) Comments With add-on SO2 control device. CEMS required under 40 CFR 60.105(a)(8-9) 25 ppmvd considered achieve-able within Consent Decrees

Third Stage Separators

Third stage separators (TSS) provide another stage of cyclonic separation in addition to the two stages of cyclones typically included within FCC regenerator vessels for environmental protection. Third stage separators have also been widely utilized in FCC applications to protect flue gas expanders from erosion by catalyst fines in the flue gas exiting the regenerator, as shown in Figure 2.
Figure 2: Third Stage Separator Controlling Particulate Emissions and Expander
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Opacity Pollutant

30% Limit 50 ppmvd or 90% reduction, whichever

40 CFR 60.102(a)(2) Reference 40 CFR 60.104(b)(1)

Sulfur Dioxide

is less stringent

9.8 lb SO2/1000 lb coke burned or no greater than 0.3 wt% feed sulfur Nickel L lb PM/1000 lb coke burn-off

40 CFR 60.104(b)(2) Or 40 CFR 60.104(b)(3)

Without add-on SO2 , Control device

See proposed 40 CFR 63 -Sub-part UU (MACT II), 13,000 mg/hr (0.029 lb/hr) of Ni. Consent Decrees 20 ppmvd considered achieve-able within Consent Decrees

Nitrogen Oxides (NOx)

NA

Notes: 1) ppmvd = parts per million, volume, dry basis corrected to 0% O2 2) 40 CFR 60 = Title 40, Code of Federal Regulations, Part 60, also known as the New Source Performance Standards. Subpart J (60.100-60.109) covers Standards of Performance for Petroleum Reneries 3) CEMS = Continuous emissions monitoring system. When concentration limits imposed, O2 per40 CFR 60.105(a)(10)

Table 3 Typical Flue Gas Particulate Concentrations for Compliance with NSPS / MACT II Several options for controlling FCC flue gas particulate, SOx and NOx emissions to meet environmental requirements are discussed in more detail below.
Regenerator Operating Mode Flue gas O2, vol% Flue gas CO2/CO, vol/vol Flue gas particulate, lb/1000 lb coke Flue gas particulate, mg/Nm3 Complete CO Combustion 1.5 8 Partial CO Combustion 0.2 5 1.0 Partial CO Combustion 0.2 2 1.0 Partial CO Combustion 0.2 1 1.0

1.0

97

109

116

124

The FCC technologies offered by Halliburton KBR include the CycloFinesTM TSS, which uses patented cyclone technology and a proprietary design to remove catalyst fines from FCC regenerator flue gas. The CycloFinesTM TSS consists of a pressure vessel containing numerous cyclone elements as depicted in Figure 3. Flue gas from the FCC regenerator enters the top of the separator where it is then distributed to the cyclone elements. The clean flue gas exits from the upper plenum chamber, while a small underflow of flue gas carries the captured particulates out the bottom of the separator. Developed by ExxonMobil and KBR in an extensive joint program that began in 1993, CycloFines TM TSS offers refiners an improved abatement technology which in many cases, can easily comply with EPA particulate emission limits(7). The CycloFinesTM TSS development program was initiated to determine if existing TSS designs that were underperforming in ExxonMobil refineries could be improved. The initial investigation led to cold flow modeling of full scale cyclone elements.

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In these tests, cyclone diameter, orientation, gas inlet, gas outlet, and proprietary configurations were optimized.

Table 4 CycloFinesTM TSS Commercial Data from ExxonMobil Altona

Operating Data Test #1 2/8/98 1315 18 299 1.4 1.5 Test #2 2/10/98 1310 17 288 1.6 1.5 Test #3 2/11/98 13601 17 295 4.6 None

Figure 3: CycloFinesTM TSS

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Temperature, F Pressure, psig Gas rate, Mlb/hr Pressure drop, psi Underow, % COLLECTION DATA Inlet loading, mg/Nm Outlet loading, mg/Nm TSS Efciency, %

81 7.3 91.0

118 10.3 91.3

109 10.2 90.6

To assure scale-up to commercial operating conditions, hot flow modeling was performed. Finally, a large scale cold flow model, which included six commercial scale cyclone elements, was also built and tested at the KBR Technology Development Center in Houston, con-cluding development of the ultra-efficient CycloFinesTM TSS. CycloFinesTM technology was first commercialized for environmental protection in September 1997 at the ExxonMobil refinery in Altona, Australia with a conventional 4th stage cyclone on the underflow. The CycloFinesTM TSS at Altona has operated very well, proving the effectiveness of the new technology in commercial operation(8). Dust surveys as summarized in Table 4 below have consistently shown that the TSS collected 90 to 91 percent of the dust and nearly all particles with diameters greater than 4 microns entering the separator. Dust concentrations at the outlet of the TSS have been measured in the range of 10 to 20 mg/Nm3. The overall system, including gas from the underflow separator, is providing an FCC stack flue gas dust content of below 30 mg/ Nm3. This loss rate equates to only 0.3 lb catalyst per 1000 lbs of coke burned, which is far lower than the MACT II particulate emission limit of 1.0 lb catalyst per 1000 lb of coke.

Not only has the CycloFinesTM TSS at Altona demonstrated the expected ultra-high efficiency during normal operation, it has also demonstrated robustness of operation during upsets in the FCC regenerator operation. The CycloFinesTM TSS efficiency exceeds the requirements of MACT II with essentially 100% capture of all particles larger than 5 microns in diameter. This extra protection may be important to future operations because the regenerator catalyst loss rate and particle size distribution may change significantly over time due to deterioration of regenerator cyclones, changes in fresh catalyst make-up rate or catalyst properties, and changes to regenerator operating conditions and other FCC operating variables.

Electrostatic Precipitators
Electrostatic precipitators (ESPs) have been used for the reduction of FCC particulate emissions since the 1940s, and modern ESPs can be designed to reduce particulate emissions to very low levels. Figure 4 depicts an ESP in a typical FCC application. ESPs consist of one or more gas tight chambers containing rows of collection plates and voltage discharge electrodes, which apply electrical charges to the particles in a waste gas stream in order to collect them before they reach the stack. ESP operation consists of three basic steps; particle charging, particle collection, and particle removal. Each step must be executed properly in order to effectively remove particulate to acceptable levels.

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Figure 4: Electrostatic Precipitator Factors Effecting ESP Performance

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size, particle resistivity, electric field, and the temperature and composition of the flue gas.

Flue Gas Properties Temperature Composition Rate (Velocity) Catalyst Properties Resistivity Particle size Collection Plate Rapping Frequency Intensity

Figure 5: ESP Particle Charging Process

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The process of charging a particle is accomplished by establishing a non-uniform electric field between the discharge electrodes and the collection plates. This non-uniform field is established by applying high voltage to the discharge electrodes, which generates electrons that flow from the discharge electrodes to the collection plates. As a result, neutral gas molecules are charged when struck by the high velocity/ high energy electrons. The flow of negatively charged gas ions and electrons is generally referred to as corona current flow (see Figure 5). As the flue gas travels through the resulting corona, suspended particles in the flue gas become charged by the negative ions, which are attracted to the surface of the particles. A measure of how readily a particle takes a charge is referred to as the particle resistivity. A highly resistive particle is difficult to charge. The resistivity of the catalyst plays a key factor in collection efficiency. Some FCC catalysts display high resistivity making it difficult to place a charge on them. If a particle is resistive to receiving an adequate charge, a greater electric field will need to be generated in order to capture this particle. If a sufficient field cannot be generated, the resistive particle will simply pass through the ESP. The particle collection process begins the moment the particle absorbs a charge sufficient enough to be attracted by the collection plates. The electric field generated by the discharge electrodes causes the charged particles to migrate towards the grounded collecting plates where they accumulate in a layer, gradually losing their charge. The factors, which affect the particle charging and collection process, include particle

Temperature and humidity, as shown in Figure 6 (9), affect the resistivity of a particle. At temperatures less than 300oF, the predominant mechanism for applying a charge is surface conduction. For this type of conduction, the charged ion is deposited on a thin surface film, which surrounds the particle. During surface conduction, the ability to charge a particle decreases as the temperature increases (10). For temperatures greater than 300oF, the effects of surface conduction decrease and volume conduction takes over. This type of conduction involves the charged ion actually being absorbed by the particle. During this process, the ability of a particle to accept a charge increases with increasing temperature. In addition, certain gas molecules, which are found in FCC flue gas, are easier to charge than others. Molecules such as nitrogen oxides, sulfur oxides, ammonia, and water readily absorb an electrical charge. Ammonia and/or water are often injected into FCC flue gas streams upstream of the ESP to increase removal efficiency (11).

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Figure 6: Effect of Flue Gas Properties on Resistivity of dust

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ments, as well as allow for process changes. Figure 7 shows a schematic of an ExxonMobil Wet Gas Scrubber(13). The flue gas enters the scrubbers where intensive contact between the gas and liquid removes both the particulates and sulfur oxides. Particulate capture occurs by inertial impaction of the liquid droplets with particles in the gas stream. Sulfur oxide removal occurs by reaction with a well known sulfite buffer. Thus, the system provides a single step removal of both pollutants.
Figure 7: Wet Gas Scrubbing Process controls both SOx And Particulates
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Upon proper rapping, a solid sheet of catalyst falls by gravity into hoppers located beneath the ESP. The second phase in particle removal is to remove the catalyst from these hoppers. Several methods to remove catalyst from hoppers are offered. These methods include gravity drop out systems, screw conveyor systems, and pneumatic/vacuum transfer systems. Bridging problems can be avoided by installing vibrators in the hopper walls. Likewise, heaters are often installed in the hopper walls to drive moisture out of the collected catalyst. Most of the ESP systems can be maintained externally without having to shut down the entire unit. In addition, a number of recent improvements have been made to ESP mechanical hardware, including rappers, electrode design, and control systems. However, if this hardware is not operated properly, taking into account how each of these systems affect each other, the particle removal efficiency of the ESP can be compromised.

Flue Gas Scrubbing

An appropriately designed flue gas scrubbing process can easily meet the Refinery NSPS particulate and SOx emission limits. As specified in the proposed MACT II rule, an FCC Unit which meets the requirements of the Refinery NSPS is considered in compliance with MACT II(12). As a result, FCC Units equipped with flue gas scrubbers will be in compliance with both MACT II and NSPS. In order to maintain their NSPS grandfathered status, many FCC Units have not undergone process modification. The installation of flue gas scubbers in these units will satisfy the MACT II require-

The clean gas is separated from the dirty liquid in the separator drum. The cleaned gas then exits to the atmosphere through a stack mounted on top of the separator drum. The scrubbing liquid is regenerated by direct addition of a sodium based chemical to the scrubber liquor and recycled back to the scrubbers. Water lost through evaporation and purge is also made up. A liquid stream may be purged from the disengaging drum to maintain an equilibrium concentration of solids and dissolved salts (products of sulfur oxide removal) within the system. The purge stream can be further treated in the Purge Treatment Unit (PTU) to reduce its Chemical Oxygen Demand (COD) and Total Suspended Solids content to environmentally acceptable levels. ExxonMobil Wet Gas Scrubbing (WGS), also offered by Halliburton KBR, is a widely commercialized FCC flue gas scrubbing technology with sixteen units in operation and additional units are planned or in construction. Flue gas scrubbing systems have demonstrated, on a long-term basis, the ability to remove particulates to very low levels. In addition, flue gas scrubbing systems have demonstrated SO2 removal in excess of 90 percent, with several demonstrating efficiencies
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above 99 percent. Operating experience has shown that dayto-day changes in flue gas rate, composition, solids loading, temperature, etc. can readily be handled, with small changes in the flue gas scrubber operating conditions.

Selective Catalytic Reduction (SCR)

SCR technology is commercially proven for reducing NOx in FCC regenerator flue gas and involves the reaction of ammonia with NOx in the presence of oxygen and catalyst. The catalyst, depicted in Figure 8, is most commonly vanadium pentoxide/titanium dioxide based(15). Other catalysts based on precious metals (platinum or palladium) or zeolites can also be used as SCR catalyst. SCRs can operate in the temperature range between 300 and 1100F (16,17) depending on the catalyst (preferably 600 to 750F for vanadium pentoxide/ titanium dioxide catalyst) and achieve greater than 90% NOx removal efficiency. A NH3/NOx molar ratio of 1.0 or slightly higher is commonly used in modern SCR systems. The reactions between NOx and ammonia on the SCR catalyst are as follows: 4 NH3 + 4 NO + O2 4 N2 + 6 H2O 4 NH3 + 2 NO2 + O2 3 N2 + 6 H2O The first reaction is the conversion of NO to nitrogen and the second reaction is the conversion of NO2 to nitrogen. One mole of ammonia is required to convert one mole of NO, whereas, 2 moles of ammonia are required to convert one mole of NO2. This means that as the NO2 concentration in the flue gas increases, the amount of ammonia required will increase. There is usually Sufficient oxygen in the flue gas without the need to supply additional oxygen.
Figure 8: SCR Catalyst Beds
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Flue Gas NOx Origin

In general, nitrogen oxides (NOx) are generated Either from thermal oxidation of nitrogen in the combustion air which is known as thermal NOx, or by oxidation of organically bound nitrogen found in a fuel known as fuel NOx. In the FCC process, fuel NOx is produced in the regenerator as result of burning nitrogen contained in coke that originates from the FCC feed (14). Very little thermal NOx is generated in FCC because of the low operating temperatures. The nitrogen oxide species presen in the regenerator are mostly in the form of NO and NO2 with higher proportion of NO. The factors that affect NOx generation in the FCCU regenerator include flue gas oxygen content, carbon on regenerated catalyst, regenerator design, combustion/particle temperature, concentration of nitrogen in coke and FCC additives such as CO promoters and SOx additives. Current methods for controlling the NOx from FCC regenerator flue gas can be grouped into the following two classifications: Post regeneration technologies such as Selective Catalytic Reduction (SCR) and Selective Non-Catalytic Reduction (SNCR). Source control technologies such as catalyst additives, feed hydrotreating, and counter-current regeneration which lower the amount of NOx produced in the FCC regenerator. FCC REGENERATOR NOX EMISSIONS NOx originates from nitrogen in the FCC feedstock. The coke contains less than 60% of the nitrogen in the FCC feedstock. Less than 30% of the nitrogen in the coke is converted to NOx in the regenerator.

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Another important reaction is the oxidation of SO2 to SO3: 2SO2 + O2 2SO3 This reaction is reversible. The SO2 conversion to SO3 is a function of temperature and the SCR catalyst formulation (V2O5 content). Irrespective of the catalyst formulation, the SO2 conversion increases with temperature in the range of interest. Unreacted NH3 leaving the SCR reacts with sulfur trioxide to form ammonium sulfate and bisulfate that deposit on downstream equipment. The key reactions for the formation of ammonium bisulfate and ammonium sulfate are shown below and data describing their formation as a function of temperature are presented in Figure 9(18). NH3 + SO3 + H2O NH4HSO4 2NH3 + SO3 + H2O (NH4)2SO4 Ammonium sulfates deposit on surfaces below 450F(19) and increase particulate emission. Ammonium sulfate is a dry particulate matter that contributes to plume formation. Ammonium bisulfate is highly acidic and sticky substance, which deposits on downstream equipment such as convection coils and air heaters or economizers resulting in pluggage and deterioration of equipment performance (19). Keeping ammonia slip low and monitoring downstream flue gas temperature can minimize deposit formation. The SCR catalyst normally consists of a ceramic substrate or a metal carrier and active ingredients dispersed in the carrier. A typical carrier is titanium dioxide (TiO2); tungsten trioxide (WO3) is also added to provide strength and thermal stability. The three popular shapes of SCR catalyst available are honeycomb, corrugated and plate. The types of ammonia available are anhydrous, aqueous and urea (CO(NH2)2). Anhydrous ammonia has a high vapor pressure at ambient temperature, and thus requires pressurized storage. It is very toxic and its release to the atmosphere may present an inhalation hazard, which makes transportation of pure anhydrous ammonia less desirable from a safety standpoint than in its aqueous form. It is also subject to risk management regulations imposed by regulatory authorities such as EPA as well as OSHA. However, the energy required to vaporize a pound of anhydrous ammonia is less than required to vaporize a pound of aqueous amonia and transportation costs are also less because of the water content.

Figure 9: Salt Formation Temperatures Ammonium - Sulfate and Bisulfate

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Aqueous ammonia, which is commonly used, is less hazardous. A typical industrial grade contains approximately 25 to 29 wt% ammonia in water. This ammonia-water mixture has a nearly atmospheric vapor pressure at ambient temperature and it can be more safely transported by road. Depending on site-specifics, storage would still be in a pressurized container and other special precautions may be taken to prevent ammonia vapor from reaching its explosive limits. Urea is not commonly used directly for SCR applications. However, urea-to-ammonia conversion systems (20) are now available and could be used where anhydrous or aqueous ammonia transportation or storage is viewed as an unacceptable risk. The current process hydrolyzes urea solution to an ammonia/CO2 gas mixture that meets the dynamic requirements of the NOx control system. For an aqueous ammonia system, the ammonia skid comprises of ammonia storage tank, ammonia injection pump, dilution air fan and heater, ammonia vaporizer and ammonia injection grid, control valves and flow meters. The aqueous ammonia is pumped, metered and sprayed into the vaporizer. It is then combined with preheated dilution air before being injected through distribution grids located in the flue gas line near the inlet of the SCR. Soot blowers are used when the SCR inlet dust loading is high to remove accumulated dust from the SCR catalyst surface. If the dust settles on the catalyst surface or enters and plugs the micropores, the SCR catalyst activity is reduced because of the unavailability of active sites. The traditional

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method of catalyst cleaning is the use of rake type soot blowers. The nozzles can be fixed or rotary. Soot blowers use either superheated steam or dry air. They can be sequenced to cycle once per shift depending on the dust loading. Sonic or acoustic horns are also being considered as alternate to steam soot blowing in SCR applications. The SCR is usually installed downstream of the waste heat boiler either before or after the electrostatic precipitator. In either case, the waste heat boiler must be modified by removing the economizer tubes or by providing hot gas bypass around it to maintain the flue gas temperature to the SCR. Ammonia slip is a term used to describe the amount of ammonia escaping unreacted from the reaction zone in the flue gas. The most important parameters considered for the design of the SCR are the interdependence between NOx reduction, ammonia slip and the catalyst volume. The required volume of catalyst increases with the design NOx removal efficiency, and for a given volume of catalyst, the NOx removal efficiency increases with ammonia slip, as shown in Figure 10(18). Careful consideration must also be given to design catalyst life and overpressure protection for the SCR. Selective Non-Catalytic Reduction (SNCR) SNCR involves the reduction of NOx with ammonia or urea in the absence of catalyst at high temperatures. The principal reactions between NOx and ammonia are: 4NH3 + 6NO 5N2 + 6H2O 8NH3 + 6NO2 7N2 +12H2O
Figure 10: SNCR Ammonia Slip Typical Performance
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Depending on the temperature, NH3 can be oxidized to produce more NO. Urea decomposes to form NH2 radicals and CO that react with NOx with the following overall reaction: CO (NH2)2 + 2NO + 0.5O2 2N2 + CO2 + 2H2O In the typical application of SNCR depicted in Figure 11(21), flue gas temperatures in the range of 1600 to 1900F are required as well as sufficient residence time at these temperatures to promote the best NOx reduction. Also, through the use of secondary reductant additions, this temperature range, which displays a characteristic peak, may be shifted to lower operating temperature ranges (22).
Figure 11: SNCR Temperature Window Typical Performance
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SNCR requires some amount of excess ammonia addition above stoichiometric requirements to achieve high NOx reduction. This requirement is due, in part, to the thermally driven ammonia consumption reactions occurring before the NOx reduction reactions. Ammonia slip in SNCR applications is typically 10 to 50 ppmv. Due to the low NOx reduction at low temperatures, SNCR is not currently used to treat flue gas from an FCC regenerator operating in complete combustion mode, with typical exhaust temperature of 1350 F. For SNCR to be most effective, the flue gas must be reheated to between 1600 to 1800 F, which would normally be cost prohibitive. In an FCC operating in partial combustion mode, an SNCR can be used to reduce NOx by applying it to the CO boiler which is normally operated above 1600 F and which has sufficient residence time at temperature to achieve SNCR goals. For this case, ammonia vapor or urea solution is injected into the combustion zone at a location most favorable for NOx removal. SCNR NOx removal efficiencies achievable can range from 30 to 70% depending upon site-specifics.
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Catalyst Additives
Platinum based CO combustion promoters are known to increase FCC NOx emissions. Non-platinum based CO combustion promoters are now available and can be used to reduce NOx generation in FCC regenerators. In commercial tests of non-platinum based CO promoters, they have reduced NOx emission by 25 to 85%(23) compared to NOx emissions while using platinum based CO promoters. Specially formulated FCC catalyst additives can also be added to the regenerator to promote the reduction of NOx formed to nitrogen and water. These catalysts promote the reduction reaction between carbon or carbon monoxide and nitrogen oxides inside the regenerator.
Figure 12: Counter-Current Regenerator Controlled Combustion
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2C + 2NO _ 2CO + N2 For a given concentration of nitrogen in coke, the KBR Orthoflow regenerator produces 60 to 80% less NOx than other types of regenerators as shown in Figure 13.
Figure 13: NOx from FCC Coke Burning Impact of regenerator design
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Conclusion
The proper choice of technology to comply with environmental requirements is greatly influenced by the specifics of the application and the overall goals of the facility. What might be a great option for one facility may not work for another. Table 5 summarizes the relative attributes of the FCC regenerator flue gas control technologies discussed in this paper and provides insight into which technology is best suited to a particular application.
Based on NSPS or MACT II Limits Particulate Control Expander Protection CO Control SOx Control NOx Control Major Utilities Consumption CyclonesTM TSS Yes Yes No No No None ESP Flue Gas Scrubbet Yes No No Yes No Caustic Soda ash Water Steam Electricity SCR SNCR No No No No Yes Ammonia Urea Catalyst Catalyst Additives No No Yes Yes Yes CounterCurrent Regen No No No No Yes

Catalyst manufacturers are currently conducting commercial tests at selected refineries to evaluate the effectiveness of NOx reducing additives. Published results indicate a broad range of NOx reduction percentages with a 40 to 50% reduction being most common(24). NOx reducing additives may be most economical in cases where the amount of NOx reduction required does not justify the installation of an SCR.

Yes No No No No Electricity

FCC Regenerator Design for Low NOx Emission

The FCC regenerator design also plays an important role in NOx emission because the percentage of nitrogen in coke converted to NOx varies widely with regenerator design. In the KBR counter-current regenerator, the coke-rich incoming spent catalyst is evenly distributed and first exposed to regeneration gas near the top of the fluid bed, as shown in Figure 12. The carbon-rich environment at the top of the fluid bed promotes the reduction of NOx to nitrogen according to the following reaction mechanism:

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References
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