Water Management in a

Petroleum Refinery
The petroleum industry

Tier 1
 The Petroleum Industry:

Crude oil refining operations involve extracting useful petroleum products

from crude oil. Crude oil contains fractions of napthas, gasoline, gas oils,
diesel fuel, asphalt, jet fuel and lubrication fuels.

Large quantities of production wastes are produced during exploration and

production:
 Wastewater

 Solid waste

 Toxic pollutants

Tier 1
 The Petroleum Industry:

Production wastes in the petroleum industry can be grouped broadly into 2

classes:
• Wastes related to drilling including chemical additives: treatment and
disposal of oil drilling wastes takes place either on or off the drilling site.
• Wastes related to oil production, primarily produced water:

The volume of produced water exceeds the volume of drilled wastes.

If environmental quality standards are not exceeded the remainder may be
discharged to surface waters.

Tier 1
 What is refinery effluent?

Petroleum refineries use large volumes of water in their processes.

The wastewater contains hazardous chemicals:

Tier 1
 Refinery wastes:

Emissions from refineries include:

 Sulfur oxides

 Nitrogen oxides

 Benzene, toluene and xylene

 VOC

 Wastewater containing BOD levels

 Heavy metals

Tier 1
 Wastes generated:

Pollution Approximate Quantities

Cooling systems 3.5-5 m3 of wastewater generated per ton of crude.

BOD 150-250 mg/l

COD 300-600 mg/l
phenol 20-200 mg/l
Polluted wastewater oil 100-300 mg/l (desalted water)
oil 5000 mg/l in tank bottom
benzene 1-100 mg/l
heavy metals 0.1-100 mg/l

3 to 5 kg per ton of crude (80 % should be considered as hazardous

Solid waste and sludge
waste because of the heavy metals and toxic organic presence).
VOC emissions 0.5 to 6 kg/ton of crude.

BTX (Benzene, Toluene and Xylene) 0.75 to 6 g/ton of crude

Others emissions Sulfur oxides 0.2-0.6 kg/ton of crude
Nitrogen oxides 0.006-0.5 kg/ton of crude

(Pollution Prevention and Abatement Handbook World Bank Group)

Tier 1
 8

• In refineries, water is a crucial

part in removal of contaminants
from crude oil
▫ Desalting
▫ Steam cracking
▫ Sweetening
▫ Hydrotreating
▫ Distillation

Crude fractionation unit

 9

Background
• Water re-use as a practical way to reduce
freshwater intake
▫ Reduces wastewater treatment costs
▫ Lessens need to comply with government
standards for pollution levels
▫ Relieves need to obtain larger amounts of
freshwater (costly and limited)
▫ Promotes a greener environment
 10

Refinery Schematic
• Highlights water-using and regeneration processes

Red: Water-using
units

Green:
Conventional
water regeneration
processes (i.e.
end-of-pipe
treatment)
 11

Water Treatment Units

• Regeneration processes*
Regeneration Type of Maximum outlet
process contaminant concentration
removed (ppm)

API Separator Organics 50

Activated Carbon Organics 50
Adsorption
Reverse Osmosis Salts 20
Waste Water H2S 5
Treatment NH3 30
Biological Treatment Organics 230
*TYPICAL REFINERY STANDARDS
 12

API Separator
• API separator
▫ Separates suspended
solids and oil from
wastewater streams
based on differences
in specific gravities
between the oil and
the wastewater

▫ Particles settle based Vt 

2
W   O gR 2
on Stokes Law 9
 13

API Separator
• Contaminant particles fall through
Buoyancy
the viscous fluid by their own weight force

• Upward drag of small particles Drag force

(assumed to be spheres) combines
with the buoyancy force balances the
gravitational force and creates a Gravity

settling velocity
 14

Wastewater Treatment
• Sour water containing H2S
and NH3 enter into a
hydrogen sulfide stripper

• Steam absorbs H2S from

passing liquid stream

• Wastewater is sent to a
distillation column where
NH3 is stripped
 15

Biological Treatment
• Microorganisms present in wastewater
will feed on the carbonaceous organic
matter in the wastewater and
repopulate in an aquatic aerobic
environment

• With a sufficient oxygen supply and an

organic material food supply, the bugs
(bacteria) will consume and metabolize
Pseudomonas the organic waste and transform it into
cell mass, which settles in the bottom of
a settling tank
 16

Activated Sludge
• Air is pumped through
the bottom of an
aeration tank
▫ Air rises and provides
oxygen to the water

• Effluent is sent through

a secondary clarifier that
separates the used
Activated Sludge schematic cellular material from
the treated wastewater
 17

Reverse Osmosis
• Dissolved solutes are
removed from a
wastewater by a pressure-
driven membrane

• High pressure applied at

the feed creates
differential pressure
between the permeate
and feed sides of the
membrane
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Reverse Osmosis
Flux of water molecules through membrane:

JW=kW (∆P - ∆π)

Where: Jw=apparent volumetric flux of water (L/m2s)

kw= mass transfer coefficient of water
molecules (L/m2s.atm)
∆P= change in external pressure (atm)
∆π= change in osmotic pressure (atm)
 19

Reverse Osmosis
• Flux of salt solute through the membrane is:

JS = ks (ΔC)

where: JS = mass flux of solute (kg/m2s)

kS = mass transfer coefficient of
solute (L-S/m2)
 20

Reverse Osmosis
• Using van’t Hoff equation, the osmotic pressure
is given as:
π=cRT
where:
c = concentration of solute in feed/permeate
(mol/L)
R = gas constant ~ 0.0820578 L.atm/(g-mol.K)
T = temperature of solution (K)
 21

Reverse Osmosis
• The flow rate of water
molecules in permeate
Q permeate  J w A

• Flux of solutes is
related to water flux
by the equation
J s  C permeate J w

• Mathcad was used to

generate data points
Mathcad snapshot- Reverse Osmosis
 22

Activated Carbon Adsorption

• A fixed bed of activated
carbon adsorbs organics
in wastewater

• The bed of activated

carbon is regenerated
using
▫ Pressure-swing
desorption
▫ Thermal-swing
desorption
 23

Activated Carbon Adsorption

• Assumptions made
▫ Isothermal and isobaric
operation
▫ Fixed bed adsorption
▫ Langmuir isotherm for
adsorption used
At equilibrium:
qmax kC 
q
1  kC 
Mass transfer zone in column
At saturation: qmax kC F
q
1  kC F