Air Pollution From Refineries

Basis: 1 Million Tonnes of Crude processed, refineries emit

20000 - 820000 T of Carbon dioxides 60 - 700 T of nitrogen oxides 10 - 3000 T of particulate matter 30 - 6000 T of sulphur oxides 50 - 6000 T of volatile organic chemicals

CO2 / CO Emissions
Power plants Process furnaces Boilers Gas turbines Heaters Fluidized Catalytic cracking regenerators Flare system Incinerators

Impact of CO2 / CO Emissions

Almost all carbon present in crude oil once produced from the oil well will be converted into CO2 sooner or later A small portion (< 3 - 10 %) of the CO2 will be converted in the refinery during the processing of crude oil into marketable products. Global climate change Link with energy efficiency CO2 is increasing as refineries are shifting to more energy intensive transportation fuels from heavy fuel oil CO is more intermediate product of combustion process when combustion is improper Regeneration of catalyst

NOx Emissions
N2O, NO and NO2 Emissions from refineries as a whole Emission from specific processes /energy systems
Power plant Furnaces Boilers Gas turbines Catalytic cracker regenerators Flares Incinerators

Fuel oil can generate about three times more NOx than gas fuels

Impact of NOx
Nitrogen in Fuel and from Nitrogen in Combustion air Mix of NO2 and NO Contributes to both greenhouse effect (global warming) and ozone depletion Oxides of nitrogen (NOx), emissions into air can combine with water and form a component of acid rain NOx in combination with volatile organic compounds and sunlight, can lead to the formation of ground-level ozone Lower emissions when deNOx treatment is applied

Nitrogen oxides abatement techniques

Selective catalytic reduction (SCR) Inlet NOx concentration to the SCR may vary from 200 2000 mg/Nm3@ 3 % O2. Inlet NOx concentrations to the SCR vary with the type of FCC used (total or partial combustion in combination with a CO boiler) and the type of feed used (heavier feed tends to produce higher NOx emissions) Reduction by 85 - 90 % of NOx emissions with the outlet concentration of NOx reduced to 30 - 250 mg/Nm3@ 3 % O2, depending on the inlet concentration Those reduction efficiencies provide a reduction of 300 tonnes of NOx per year from catcrackers of capacity of 1.65 Mt/yr. Other advantage is that some CO oxidation also occurs in the SCR process (aprox. 40%).

Nitrogen oxides abatement techniques Selective non-catalytic reduction (SNCR)

These systems reduce the NOx emissions by 40 - 80 %. The outlet concentrations can be down to <200 - 400 mg/Nm3@ 3 % O2 depending on the nitrogen content of the feedstock. Instead of ammonia, urea can be also used. The use of urea has the advantage to be more soluble in water and consequently reduce the risk handling/storage of NH3. Use of NH3 (storage/handling), risk of NH3 emissions when operating outside stoichiometric proportion. Ammonia needed for this technique may be supplied by two-stage sour water strippers. The use of urea generates more ammonia (from urea) slip and some N2O formation. High temperatures (800 - 900 C) of the flue gases are needed. It is applicable in partial combustion FCCs with CO boiler; retrofitting in existing CO boilers is relatively simple. It is also applicable to full combustion units. Space requirements are mainly related to NH3 storage.

SOx Emissions
Energy systems such as
Fuels containing sulphur compounds Catalytic cracker regenerators Bitumen production Coking processes Amine treating Sulphur recovery units Flares

Sulphur in products from refinery Sulphur balance as part of Environmental Management System

Impact of SOx Emissions

Fuel with 1% sulphur generates a flue gas with 1700 mg/Nm3 Sox emissions into air can combine with water and form a component of acid rain Sulphur in the fuel is transformed to a mix of SO2 and SO3 Emission limit governed by regulations

VOC Emissions
Generic term for all compounds containing organic carbon which evaporate at ambient temperature Mostly fugitive emissions mainly from evaporation of leakage of hydrocarbon fractions during storage , product loading, handling and distribution Vents, flares, seals from pumps, compressors, flanges, valves, seals and drains, wastewater, storage tanks (tank breathing) Wastewater systems (oil/water separation systems, air stripping in floatation units and bioreactor) Non-optimal combustion conditions minor VOC emissions from storage tanks account for more than 40% of total emissions

Factors Driving VOC Emissions

Valves that are operated frequently, such as control valves, may wear more quickly and will allow emission paths to develop Newer, low-leak control valves provide good fugitive emissions control performance. Valves with rising stems (gate valves, globe valves) are likely to leak more frequently than quarter-turn type valves such as ball and plug valves. Equipment design, quality of the sealing system, maintenance programme and properties of the line contents also impact VOC emissions Poorer designs (with wider tolerances), poor sealing systems (e.g. leak-prone valve packings) and limited maintenance will lead to higher emissions.

HC Emission from wastewater Systems

Exposed surface area of the oilcontaminated untreated water tank (API separator) Oil evaporation factor (empirical)
20 g/m2 per hour for open oil separator 2 g/m2 per hour for covered oil separator 2 g/m2 per hour for flotation 0.2 g/m2 per hour for biological treatments

Impact of VOC emissions

Volatile organic carbons (VOC), can react with NOx in the presence of sunlight to form low-level atmospheric ozone. Emissions of VOC can give rise to odour problems, which may result in complaints from nearby residents.

Particulate emissions
Particulates (Catalyst changeovers and cokers) Metals as constituents of the particulates (Vanadium, Nickel, Arsenic, Mercury) Main emission sources are
Process furnaces/ boilers (fired with liquid heavy fuel oil ~500 to 1000 mg/Nm3 and for new optimal burner with steam atomization ~200 mg/Nm3) Catalytic cracker regenerators (fines10 m max) Coke plants Incinerators Decoking Soot blowing of furnaces (2000 mg/Nm3) Flare

Particulate Matter Forms

Soot: particle size is below 1 m- visible smoke from a stack is caused by all particles but mainly those with a particle size between 0.5 and 5 m Cenospheres: they originate from the liquid phase wastes of combustion of heavy oil droplets at relatively low temperature (< 700 C). The size is equal to or larger than that of the original oil droplets Coke particles, formed through liquid phase cracking in combustion at high temperatures (>700 C) -particle size is generally from 1 to 10 m Fine particles (< 0.01 m): their contribution to the total mass emission is negligible.

Impact of Particulate emissions

The concern with particulate emissions (including of heavy metals) stems from health effects. Range of emissions found in refineries is from 100 to 20000 tonnes of particulates emitted per year Specific emission range found is from 10 to 3000 tonnes of particulates per million tonnes of crude oil processed. Lower emission value can be achieved in simple refineries burning substantial amounts of gas or when effective dedusting devices (ESP, bag filters) are installed.

Particulate abatement techniques

The selection of the catalyst can be seen as a particulate abatement technique. Additional cyclones Highly specialised cyclones are used (third-stage and multicyclones), which are designed to suit the arrangement, dimensions, contours, velocities, pressures and densities of the particles to be removed. This is the natural first choice of clean-up device for particulates: these are conventional cyclones, fitted externally to the regenerator but operating on the same principle as the internal first and second cyclones. They are high-velocity devices and recovered catalyst is returned to a dust hopper. By reducing the particulate content in the air, the metal emissions are reduced. Depending on the above factors, cyclones are generally efficient at removing particles in the range of 10 to 40 microns and above. Efficiencies can range from 30 to 90 %. An average performance figure for cyclone separation alone is in the region of 100 - 400 mg/Nm3. (Inlet concentration from 400 - 1000 mg/Nm3). Lower concentrations are not achievable because inlet velocities to the cyclones are in the region that causes additional attrition, which produces additional fines that pass the cyclone. The fine catalyst disposal is 300 - 400 tonnes/yr per unit. Cyclones are more effective for coarser particles and they have been designed essentially to prevent any particles greater than 10 microns from entering downstream facilities.

Electrostatic precipitators
Description A short description of an electrostatic precipitator can be found in Section 4.23.4. Achieved environmental benefits Typical particulate emission levels achieved with electrostatic precipitators range from 10 - <50 mg/Nm3 of particulate matter in the flue gas of the FCC regenerator. This level is based on averaged continuous monitoring, excluding soot blowing. The range depends on the type of catalysts, the mode of FCC operation and whether other pretreatment techniques are implemented before the ESP. Particulate abatement measures in FCC with electrostatic precipitators with efficiency greater than 99.8 %. Efficiency is not dependent on particulate size or on flue gas velocity and the pressure drop is very marginal. As a consequence of the particulate reduction, the metals (Ni, Sb, V and their components) can be reduced to less than 1 mg/Nm3 (given as Ni, Sb and V total) and, within that, Ni and its components can be reduced to less than 0.3 mg/Nm3 (given as Ni). (Half-hourly mean values attainable in continuous operation and with soot blowing in the CO boiler). Particulate emissions from the FCC can thus be reduced to 1.1 - 2.3 kg/h.

Other Emissions
H2S NH3 BTX CS2 COS HF

Abatement of H2S Emissions

Amine scrubbing system Sulphur recovery unit to convert H2S into sulphur, a byproduct produced within refineries Flaring

STORAGE AND HANDLING

Pressure vessels are normally used to store gases at high pressures (>91 kPa, e.g. LPG). Fixed roof tanks can be open to atmosphere, or designed as a pressure tank, with several classes of allowed pressure build-up, from 20 mbarg (low pressure) to 60 mbarg (high pressure). The pressure tanks are provided with Pressure/Vacuum Relief Valves to prevent explosions and implosions, the vacuum setting being -6 mbarg. Floating roof tanks are constructed in such way that the roof floats on the liquid, and moves with the liquid level (>14kPa to < 91 kPa). Above-ground storage tanks (ASTs) are used at refineries for holding either the raw feedstock (crude oil) or end-products generated by the refinery processes (gasoline, diesel, fuel oils etc.). Underground storage tanks are used much less frequently (if at all) at refineries - primarily for storing fuel for onsite boilers and vehicles, or for capturing liquids at low level drain points.

Flaring
Source gas reduction measures to the maximum extent possible; Use of efficient flare tips, and optimization of the size and number of burning nozzles Maximizing flare combustion efficiency by controlling and optimizing flare fuel / air/ steam flow rates to ensure the correct ratio of assist stream to flare stream Minimizing flaring from purges and pilots, without compromising safety through measures induding installation of purge gas reduction devices, flare gas recovery units, inert purge gas, soft seat valve technology where appropriate, and installation of conservation pilots Minimizing risk of pilot blow-out by ensuring sufficient exit velocity and providing wind guards; Use of a reliable pilot ignition system. Installation of high integray instrument pressure protection systems, where appropriate to reduce over pressure events and avoid or reduce flaring situations, Installation of knock-out drums to prevent condensate emissions, where appropriate. Minimizing liquid carry.over and entrainment in the gas flare stream with a suitable liquid separation system: Minimizing flame lift off and for flame lick; Operating flare to control odor and visible smoke emissions