Petroleum Refining Fourth Year Dr.Aysar T.

Jarullah

Safety and Environmental Aspects in Refining

The evolution of petroleum refining from simple distillation to today’s sophisticated
processes has created a need for environmental, health and safety management procedures
and safe work practices. The safe processing of crude oil into flammable gases and liquids at
high temperatures and pressures using vessels, equipment and piping requires considerable
control technologies to avoid damage to the environment. Environment andhealth
professionals assure that potential physical, mechanical, chemical and health hazards are
recognized and therefore, provisions are made for safe operating practices and appropriate
protective measures. These procedures should be established to assure compliance with
applicable regulations and standards such as hazard communications, emission rates
regulations, waste management and waste minimization.

1-Air Quality
In the 1970s and 1980s, environmental laws compelled refineries to reduce emissions of SOx,
NOx, CO2, and hydrocarbons. In the atmosphere, SOx reacts with water vapor to make
sulfurous and sulfuric acids, which return to earth as acid rain. Volatile hydrocarbons react
with NOx to make ozone. CO2 is a major “green-house” gas. To reduce these pollutants, the
industry tightened its operation by:

• Reducing fugitive hydrocarbon emissions from valves and fittings

• Removing sulfur from refinery streams and finished products
• Adding tail-gas units to sulfur recovery plants
• Reducing the production of NOx in fired heaters
• Scrubbing SOx and NOx from flue gases
• Reducing the production of CO2 by increasing energy efficiency

1.1 Sulfur Recovery

Conversion processes, hydrotreaters, and sweetening units remove chemically bound
sulfur from petroleum fractions. That’s a good thing, but where does the sulfur go? The
answer depends upon the form in which it is produced.
SOx Abatement. Fuel-oil fired heaters and the regenerators of FCC units are major sources
of refinery SOx and NOx emissions. The most obvious way to reduce SOx emissions
from a heater is to use low-sulfur fuels. Unfortunately, although that solution
requires no investment, it is probably the most expensive due to the relatively high cost of
buying low-sulfur fuel oil or hydrotreating high-sulfur fuel oil. A large fraction of the sulfur
in the feed to an FCC unit ends up in coke on the catalyst. SOx is formed in the regenerator
when the coke is burned away. Therefore, removing sulfur from the feed decreases SOx
emissions. As stated previously, using a hydrotreater or hydrocracker for feed HDS
eliminates or minimizes the cost of post-FCC desulfurization equipment. Removing basic
nitrogen decreases deactivation of acid sites on the FCC catalyst, which allows the
FCC to reach a given conversion at lower temperatures. The saturation of aromatics in
the feed pretreater provides the biggest benefit, because it converts hard-to-crack aromatics
into easier-to-crack naphthenes. This alone can justify the installation of an FCC feed
pretreater. Therefore, in addition to abating SOx, hydrotreating the feed to an FCC can
generate a substantial return.

SOx Transfer Additives. Arguably, SOx transfer additives are the most cost-effective
way to lower SOx emissions in an FCC unit. These materials, first developed by Davison
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Chemical, react with SOx in the FCC regenerator to form sulfates. When the sulfated
additive circulates to the riser/reactor section, the sulfate is reduced to H2S, which is
recovered by amine absorption and sent to the sulfur plant. In some units, these additives
reduce FCC SOx emissions by more than 70%. Consequently, if a pre-treater or post-treater
still must be installed, its size can be reduced.

Flue-Gas (Stack-Gas) Scrubbing. Flue-gas scrubbing is a refiner’s last chance to keep NOx
and SOx out of the air. In wet flue-gas desulfurization, gas streams containing SOx react with
an aqueous slurry containing calcium hydroxide Ca(OH)2 and calcium carbonate CaCO3 .
Reaction products include calcium sulfite (CaSO3) and calcium sulfate (CaSO4), which
precipitate from the solution.
NOx removal is more difficult. Wet flue-gas scrubbing removes about 20% of the NOx from
a typical FCC flue gas. To remove the rest, chemical reducing agents are used. In the
Selective Catalytic Reduction (SCR) process, anhydrous ammonia is injected into the flue gas
as it passes through a bed of catalyst at 500 to 950°F (260 to 510°C). The chemical reaction
between NOx and ammonia produces N2 and H2O.

Hydrogen Sulfide Removal. When sulfur-containing feeds pass through hydrotreaters or

conversion units, some or most of the sulfur is converted into H2S, which eventually ends up
in off-gas streams. Amine absorbers remove the H2S, leaving only 10 to 20 wppm in the
treated gas streams. H2S is steam-stripped from the amines, which are returned to the
absorbers. The H2S goes to the refinery sulfur plant.

2.1 Waste Water Treatment

Waste water treatment is used to purify process water, runoff, and sewage. As much as
possible, purified waste-water steams are re-used in the refinery. Wastewater streams may
contain suspended solids, dissolved salts, phenols, ammonia, sulfides, and other compounds.
The streams come from just about every process unit, especially those that use wash water,
condensate, stripping water, caustic, or neutralization acids.

2.1.1 Primary Treatment

Primary treatment uses a settling pond to allow most hydrocarbons and suspended
solids to separate from the wastewater. The solids drift to the bottom of the pond,
hydrocarbons are skimmed off the top, and oily sludge is removed. Difficult oil-in-water
emulsions are heated to expedite separation. Acidic wastewater is neutralized with
ammonia, lime, or sodium carbonate. Alkaline wastewater is treated with sulfuric acid,
hydrochloric acid, carbon dioxide-rich flue gas, or sulfur.

2.1.2 Secondary Treatment

Some suspended solids remain in the water after primary treatment. These are removed by
filtration, sedimentation or air flotation. Flocculation agents may be added to consolidate
the solids, making them easier to remove by sedimentation or filtration. Activated
sludge is used to digest water-soluble organic compounds, either in aerated or anaerobic
lagoons. Steam-stripping is used to remove sulfides and/or ammonia, and solvent
extraction is used to remove phenols.

2.1.3 Tertiary Treatment

Tertiary treatment processes remove specific pollutants, including traces of benzene and other
partially soluble hydrocarbons. Tertiary water treatment can include ion exchange,
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

chlorination, ozonation, reverse osmosis, or adsorption onto activated carbon. Compressed

oxygen may be used to enhance oxidation. Spraying the water into the air or bubbling air
through the water removes remaining traces of volatile chemicals such as phenol and
ammonia.

3.3 Solid Waste

Refinery solid wastes may include the following materials:
• Spent catalyst and catalyst fines
• Acid sludge from alkylation units
• Miscellaneous oil-contaminated solids
All oil-contaminated solids are treated as hazardous and sent to sanitary landfills.
Recently, super-critical extraction with carbon dioxide has been used with great success to
remove oil from contaminated dirt.

Wastes in Refinery Units

1- Desalter
Hydrogen sulphide is emitted to a atmosphere from the desalter when treating sour crude.
Demulsifiers and other chemicals, which are used in the pretreatment process, are considered
chemical hazards either during processing or in disposal. Safe material handling will
minimize human exposure to these chemicals. The wash water from the desalter unit contains
a large amount of chlorides, sulphides, ammonia, hydrocarbons and suspended solids. The
best practices should be followed to deal with this hazardous waste.

2- Crude Distillation
Low boiling point hydrocarbons can escape to the atmosphere from the leaky connections
during distillation. Hydrogen sulphide is emitted when sour crude is processed. Wastewater
contains soluble hydrocarbons, mercaptans, antifoam and anticorrosion additives.

3- Catalytic Reforming and Isomerization

Benzene is one of the most carcinogenic compounds that may be formed in an undesired
reaction in catalytic reforming. Small emissions of carbon monoxide and hydrogen sulphide
may occur during regeneration of a catalyst. Appropriate catalyst handling will prevent dust
emissions during loading. In isomerization, there is a potential for exposure to hydrogen gas,
hydrochloric acid, and hydrogen chloride and to dust when solid catalyst is used.

4- Thermal Cracking and Coking

In delayed coking units, the main point sources for air quality concerns are the coker furnace
stack emissions and the flare system where off gas is rejected from the unit and burned.
Complete combustion in both the furnace and the flare assures minimum hydrocarbon
emissions to the atmosphere. To reduce furnace stack emissions, it is important to operate
coker furnaces at optimum conditions; installing air pre-heaters and advanced process
controls can increase the overall furnace efficiency. Water, which is used for cooling, is
considered waste since it contains coke and hydrocarbons. Wastewater may be highly
alkaline and contain oil, sulphides, ammonia, and/or phenol. Large quantities of water are
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

used during coke drum cleaning. Coke handling and dewatering operations use the optimum
water quantities to reduce water pollution. Typically, all coke handling water is recycled
within the unit.

5- Hydrocracking
Low boiling point hydrocarbons, hydrogen and hydrogen sulphide can leak during
hydrocracking. Improper catalyst regeneration may lead to carbon monoxide and
hydrocarbon emissions. Steam stripping and regeneration of the catalyst create waste streams
containing sour water and ammonia.

6- Hydrotreating
Hydrogen sulphide and ammonia are hazardous emissions that are released into the
atmosphere during hydrotreating. The hydrogen required in hydrotreating reactions should be
handled with care to avoid explosions.

7- Fluid Catalytic Cracking (FCC)

Catalyst regeneration produces emissions to the atmosphere upon burning the deposited coke.
When the catalyst is stripped with steam, condensate is produced that needs to be treated
before disposing since it contains heavy metals such as nickel and vanadium. Carbon
monoxide (CO) results from the incomplete combustion of coke in the regenerator.
Combustion promoters with a noble metal base (Pd or Pt) are added to the catalyst.
Particulate matters emissions are controlled by applying more resistant catalyst and improve
cyclone designs as well as installing third stage cyclone, electrostatic precipitations and wet
scrubbers downstream from the FCC regenerator.

8- Alkylation
Sulphuric acid and hydrofluoric acid are potentially hazardous chemicals. Material handling
should be based on available material safety data sheets for both acids. Water contamination
with these acids is hazardous and may lead to an explosion. Furthermore, appropriate skin
and respiratory personal protective equipment is needed for potential exposure to liquid
spillage of the acids.

9-Asphalt Production, Solvent Extraction and Dewaxing

Phenol, amines and other solvents used in deasphalting processes are considered hazardous
chemicals. If a spill or release occurs, there is a potential for exposure to residues and asphalt.
The potential for exposure to hydrogen sulphide and sulphur dioxide exists in the production
of asphalt. Solid waste effluent should be treated with care since it contains large quantities of
hazardous chemicals.

Fugitive Emissions
Valves, flanges and fittings can emit hydrocarbons into the atmosphere. These emissions are
usually the result of improper fit, wear and tear, and corrosion. The hydrocarbon emissions
can be estimated for existing facilities using a factor that is multiplied by the number of
active equipment pieces. Generally, fugitive emissions are less than 1% of the total emissions
from tanks and flares. Where no screening values are available for particular equipment
types, average emission factors should be used. This methodology involves applying the
following equation to estimate emissions from all sources in a stream:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

where EVOC is the emission rate of VOC from all sources in kg/year, FA is the applicable
average emission factor, WFVOC is the average weight fraction of VOC in the stream, and N
is the number of pieces of equipment grouped in the relevant category according to weight
fraction of VOC. The following steps for fugitive emission calculation are:
1. Develop an inventory of the number and type of fugitive sources: The number and
service type of each equipment in the refinery must be determined.
2. Group the inventory into streams: To simplify calculations, it is recommended that the
equipment/service mode combinations identified in Step 1 (i.e. valves in gas service) be
grouped into streams according to the approximate weight fraction of VOC in each stream.
3. Note operational hours: The number of operational hours needs to be estimated.
4. Use emission factors to estimate emission rates: Use the relevant emission factors and the
equation given above to calculate the emissions from each equipment type. These emissions
should then be added to derive a total emission rate for all equipment pieces quantified using
this methodology.
Table below presents the emission factors required to estimate emissions using the steps
discussed above.

Example
In the calculations of fugitive emissions from a refinery site, the following inventory steps are
carried out:
1. A particular section of a refinery has a count of 300 valves (Step 1)
2. It is ascertained that 200 of these are in gas service (Step 1)
3. Within these valves in gas service, it is ascertained that 100 (N =100) valves are with 80
wt% (non-methane hydrocarbons) (WFVOC = 0.8) and 20 wt% methane. Therefore, the rest
of the valves do not emit any VOCs and will not be included (Step 2)
4. It is estimated that this group of valves operates for 5500 h/year (Step 3)
5. The appropriate emission factor for valves in gas service is FA = 0.0268 kg/h/source
(from Table above) (Step 4). Calculate the emission rate of VOC.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Solution:
The final emission estimate for the group of 100 valves specified above is calculated from
equation above
EVOC = (0.0268) (0.8) (100) (5500) = 11,790 kg VOC/year.

Emission Estimation
Mass balance involves the quantification of total materials into and out of a process. The
differences between their inputs and outputs are accounted for in terms of releases to the
environment or as part of the facility waste. Mass balance is particularly useful when the
input and output streams can be quantified, and this is most often the case for individual
process units and operations.
In general, emission factors are developed for emission rate estimation. The emission rate is
calculated by multiplying the emission factor by the flow rate of the activity. The formula is

Table below lists typical emission factors for refinery units.

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah