Chapter 4 - 2 Downstream Pollution Control

CHAPTER 4.
2: Downstream
Pollution Control
CHAPTER 4: DOWNSTREAM POLLUTION PREVENTION AND WASTE
MANAGEMENT
1 2 3
Explain the impacts of the Discuss the benefits of Justify the choice of
generated wastes from the pollution prevention and appropriate pollution control
major sectors of oil and gas waste management measures based on the type
industry to the environment techniques in oil and gas of waste as well as adhering
and human health. (Chapter industry according to the to the Environmental Quality
1) three P’s of sustainability Act (2012) and its related
(People, Planet, Profit). regulations.
Course Outcomes
To understand the impact of
pollution from a downstream
activity to the environment,
people and economy.
Learning outcomes
(LO) for Chapter 3 To decide the appropriate
pollution control or waste
minimisation measures for
any downstream activity.
CGE686/Chapter 4.2/PNFMK
Refinery Input/Output
Air emissions
Crude oil Products
Effluent Solid waste
Control of Atmospheric Emissions
Clean Air Regulation 1978 (Malaysia)
Clean Air Regulation (Malaysia)
Atmospheric emission control
• Point source emissions • Fugitive

emissions
Fugitive emissions control
1. Losses from pump seals, flanges etc are best controlled by

properly scheduled maintenance procedures.
• Follow the guidelines published by DOE.
2. Losses of methane and ethane from crude or process stream
preheat furnaces that uses these hydrocarbon as fuels are
overcome by using excess air to avoid incomplete combustion.
• Uses a continuous oxygen analyser to monitor the flue gases.
Pressure vessels control
• Potential hydrocarbon losses from overpressure is controlled in two

steps.
1. Staged computer alerts and/or manual alarms to provide
correction of the condition.
2. If the overpressure exceeds second set point, pressure relief valve
(PRV) vent the contents of the vessel to a flare release system.
Flare system control
• Flare system is a means of controlled burning.

• Controlled burning - burning HC vapors at a nonhazardous
point to avoid fire or explosion risks.
• Smoke problems are overcome with
• Steam injection at appropriate points in the flare systems
• To promote good fuel-air mixing.
• Good steam:HC (0.3:1) - reduces soot formation
• Option of energy recovery or recycle is possible
Flare system
Continuous emissions monitoring system (CEMS)
Incomplete
combustion forms
CEMS system
• CEMS helps to comply
emissions standards.
• Monitor
• Provide data to ensure
amount of excess air needed
for optimal combustion
• Hence, cost saving
Storage tanks emission control
• Tanks containing volatile liquids are frequently vented to
prevent over pressuring especially on a hot day.
Collapse from vapor

condensation and
atmospheric
pressure acting on
the outside of the
tank during a cold
night
Rupture
Storage tanks emission control
1. Floating roofs – hence eliminating the vapor

space (fixed roof tank)
2. Placing hollow polyethylene spheres (2 – 3
layers deep) to decrease losses from the
vapor space by 90%.
3. Increase the pressure in the tank slightly
Hollow Polyethylene Spheres
Sulfide control: Removal of sulfide from crude oil
• Objectives:
1. To reduce SO2
emissions from
refinery products
usage.
2. It is vital to
remove sulfur for
naptha streams
as sulfur poisons
the noble metal
catalysts in the
catalytic
reforming units
Schematic diagram of a typical Hydrodesulfurization (HDS) unit in a petroleum refinery

Sulfide control: Removal of sulfur from sour gas
• Typical amine treating units

used in refinery, natural
gas processing units and
other industrial facilities.
• Also known as gas
sweetening process.
Conversion of removed sulfur into elemental sulfur
• Claus process
Control of NO emissions
• Formation of NO can be kept to a minimum
1. Ensure the supply of excess air to combustion
units is at a minimum value for safe complete
combustion
2. Injection of ammonia (reducing agent) into
flue gas
3. Two-stage combustion
i. Fuel-rich - producing a relatively low
temperature; oxygen deficient, therefore
moderate amounts of fuel NOx are
formed.
ii. Air-rich - The temperature is low enough
that the formation of NO is small.
Control of carbon monoxide emission
• Source
• Catalytic regenerators from catalytic cracking units
• CO is a valuable industrial fuel
• May be burned in a ‘CO boiler’ to recover energy as steam and
CO2.
Control of solid particles
• Control of catalyst particles
losses from the cracker and
regenerator of fluid catalytic
cracking units
• Cyclones
• Electrostatic precipitator
• The metal contents are
recovered for reuse
Control of solid particles
Electrostatic precipitator
Cyclone
Control of Aqueous Emissions
Industrial Effluent Regulation 2009 (Malaysia)
Industrial Effluent Regulation 2009 (Malaysia)
Usage of water in refinery
•process water • boiler feedwater makeup

• desalter makeup • cooling water makeup
• coker quench water • potable water
• coker cutting water
• fire water
• flare seal drum
• utility water
• FCC scrubbers
• hydrotreaters
1. Water minimization project
• Aim for zero liquid discharge
http://www.perf.org/images/Archive_Refining_Water.pdf
Treatment to recycle water
• Filtration
Sand Filter
• Sand filters
• Membrane (MF, UF, RO)
• Ion exchange
RO
Membrane
Units
Re-Use non-contaminated stormwater
1. Fire water
2. Cooling water and boiler feedwater makeup
• May need to pretreated
• Removal of particulates
• Removal of Ca and Mg
3. Utility water
2. Typical Refinery Wastewater Treatment
• ‘Slop oil’ are oil droplets >
Aqueous desalter effluent 0.15 mm.
• Routed to off-specification
American Petroluem liquid oil stream for
• Desalter unit is to Institute (API) Oil reprocessing.
remove salt from Separator
crude oil
• First process in
refinery
• Effluent contains
• Sediment
• Oil • Average oil
• Dissolved salts droplet size is
about 0.06
• Sulfides mm
4. Bubbles rise
together with fine
Dissolved air flotation 3. Formation of fine particles
bubbles
• To remove finer oil
droplets. 5. Sludge is removed
from the top
• Enhancement of oil
removal can be done
by the addition of
flocculants.
• Flocculants – chemical
that promote the
aggregation of small
particles.
2. Release of
pressured air 1. Saturation of
saturated water into air in water
atmospheric pressure
Flocculation
Biological Treatment: Aerobic Treatment
Fixed Growth:
Trickling filter
Trickling filters are notable
for the diversity of life forms
that participate in
wastewater treatment,
making this process
relatively more complex
than the activated sludge
process.
Fixed Growth: Rotating
biological contactors (RBC)
• The disks are most commonly made of high-
density polyethylene or styrofoam and are
usually ridged, corrugated, or lattice-like to
increase the available surface area.
Suspended Growth –
Activated Sludge Process
Activated Sludge is a treatment process:
• that uses millions of micro-organisms
• where they live, grow and work….
• and remove BOD/COD
FIVE Principles of Activated Sludge Process
1
3
2
4 5
FIVE Principles of Activated Sludge Process
Principle Justification
1 To provide an aerobic condition (aeration reactor) for microbes to

degrade pollutants and grow. The mixture of wastewater and
microbes are called mixed liquor.
2 To provide oxygen (aeration) for microbes and sufficient mixing to
keep the microbes in suspension.
3 To separate microbes from treated water. Microbes settle at the

bottom of clarifier. The watery mixture of microbes is called
activated sludge.
4 To return part of activated sludge into aeration reactor in order to
replenish and maintain the concentration of microbes. This is called
return activated sludge or RAS.
5 To remove part of activates sludge as not to overload (to maintain
F/M ratio) the aeration reactor. The sludge is called waste activated
sludge or WAS.
F/M = Food (Soluble BOD or COD)/Microorganism

1. The workers in mixed liquor
Stalked ciliates
Pseudomonas
aeruoginosa
Nitrobacter
winogradskyi Nb-255
Rotifers
Free swimming
ciliates
2. Workers need oxygen!
Oxygen (Air)
• Required for synthesis and respiration, also for mixing
• Target for about 1-2 mg/L dissolved oxygen (DO) in aeration tank
• Target for 0.5 mg/l in clarifier
• Can be controlled by Operator
Air diffusers
Fine bubbles
Submersible
diffusers
Jet aerators
Surface
CGE686/Chapter 4.2/PNFMK aerators
Workers other requirements
• Loading – prevent “shock” loading
• Equalization tank important.
• Shock loading will cause disturbance in workers population.
• Need acclimatization period for the population to give the required efficiency.
• pH
• Optimum range 6.8 – 7.4.
• Toxicity
• Sudden drop in nematode population is often the first indication of a toxic
condition.
• Temperature
• Optimum range 20 - 40°C.
• Nutrients
• Require macronutrient such nitrogen and phosphorus. Nematode
• Approximate ratio: C:N:P = 100:5:1.
Foam in aeration reactor
White foam during start up
of ABF wastewater
• Foaming in aeration treatment plant
reactor is an
indication of its
condition.
White, stiff, billowing or

sudsy foam from very young
sludge during start up of a
new plant.
Tan foam on healthy
biomass
Modest amount of fresh

tan foam. A sign of a
well operated process.
Can be due to many Thick, greasy dark-tan to black
foam.
reasons.
• Nocardia species is
dominant
• Low dissolved oxygen
• Low F/M PROBLEM!!!
• Inappropriate sludge age
• Oil and grease carryover
3. Separation of mix liquor
• To get good separation
• Many good workers are required
• Small amount of bad workers are also required
Good Biofloc
Poor biofloc
Sludge bulking
Sludge Dewatering Units
Belt Press
Sludge Volume Reduction
• To further reduce the volume of sludge

• Can be done by:
• Dryer
• Incineration
Incinerator
Sludge dryer
Dried sludge
Refinery solid waste disposal
Options
Recover and Disposal

• Deep well disposal
Reuse OR • Incineration
whenever feasible • Precipitation
• Landfill
Non-oily Oily
• Reprocessed • Landfarming
to recover • Adding
valuable fertilizer and
materials suitable
Sludges
• Incinerate mixed culture
• Landfarming of bacteria
• Bio-treatment increase the
degradation
• Deep well
rate
injection
Neutralized
Spent acids
Routed to normal
effluent treatment
before discharge
Others
Regenerated
Spent catalyst
Reprocessed to
recover metals
Summary
CEMS
CEMS, Water
minimisation
Water
minimisation
CO
References
1. Hocking M., Handbook of Chemical Technology and Pollution

Control, 1993, Academic Press, USA.
2. http://www.perf.org/images/Archive_Refining_Water.pdf

Chapter 4 - 2 Downstream Pollution Control

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Chapter 4 - 2 Downstream Pollution Control

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CHAPTER 4.

Crude oil Products

Effluent Solid waste

• Point source emissions • Fugitive

1. Losses from pump seals, flanges etc are best controlled by

• Potential hydrocarbon losses from overpressure is controlled in two

• Flare system is a means of controlled burning.

Collapse from vapor

1. Floating roofs – hence eliminating the vapor

Hollow Polyethylene Spheres

Schematic diagram of a typical Hydrodesulfurization (HDS) unit in a petroleum refinery

• Typical amine treating units

•process water • boiler feedwater makeup

• Aim for zero liquid discharge

1 To provide an aerobic condition (aeration reactor) for microbes to

3 To separate microbes from treated water. Microbes settle at the

F/M = Food (Soluble BOD or COD)/Microorganism

White, stiff, billowing or

Modest amount of fresh

• To further reduce the volume of sludge

Recover and Disposal

1. Hocking M., Handbook of Chemical Technology and Pollution

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