INTRODUCTION TO

REFINERY PROCESS
CHEMICALS
MODULE NO. : TECH019

Confidential

Istiyarso
Oil and Gas Business Unit

2021
Refinery Process Chemicals
▪ This presentation is an attempt to introduce refinery processes, potential problems and
potential chemical applications within a complex integrated refinery.

▪ Because of the complexity within a refinery, it is not possible to present a complete

overview, however, the main problem areas have been highlighted together with
respective chemical treatment programmes, i.e. Demulsification, Corrosion,
Fouling, Foaming and ‘Others.’

▪ The above treatment programmes are identified in the schematic process flows as
follows:

Demulsifier Corrosion Inhibitor [Filming & Neutralising Amines]

Antifoulant Antifoam

‘Other’ – Biocides, Antiscalants, Scavengers etc

Typical Refinery Unit
Crude/Intermed.
Furfural and
Storage
NMP Units LPG

Naphtha Reformate
Hydrotreating Reforming
Unit (HTU) Unit Gasoline

Mid Distillate Hydrodesulphuriser Kerosene, Diesel, No. 2 Fuel Oil

Crude Unit
Unit (HDS)
(Atmospheric)

Product Blending
Jet Fuel

(Oil Movement)
Hydrocracking
Atm Gas Oil Unit
Reduced Crude

Furfural and
Alkylation Alkylate Diesel
NMP Units
Unit

Lube Oil
Light Ends
Fluid Catalytic Furnace Oil
Cracking Unit
Vac Gas Oil
(FCCU) Cracked Gasoline, Lt Cycle Oil, Slurry Oil
Vacuum Unit
Asphalt No. 6 FO
Coker Gas Oil

Bottoms
Visbreaker
Unit Sour Gas Amine Sulphur Sulphur
Unit Unit

Sour Water
Stripper
Delayed Coking
Unit Coke Coke
 Confidential

Istiyarso
Oil and Gas Business Unit

2021

CRUDE OIL STORAGE

Crude Oil Storage

PIPELINE

INTERMEDIATE CRUDE
BARGE
STORAGE STORAGE

TO CRUDE
SHIP
UNIT

RECOVERED OIL

API
SKIMMED SEPARATOR OILY
OIL WATER

SLOP OIL
SYSTEM
Emulsions:

WATER & Corrosion:

SOLIDS
Fouling:

Foaming:

Other:
 Crude Oil Storage - Process
Process:

Crude Oil: The storage function of the crude unit system is considered a refinery process because
Storage it allows steady and continuous operation of the refinery complex.

There are three basic types of storage tanks used in a refinery :

. Cone Roof Tank

. Floating Roof Tank
. Spherical Tank

Intermediate:Storage of intermediate and finished products is provided to allow uniform and

/Fin Product uninterrupted operation of refinery processes. It also allows the accumulation of
Storage products for sale. Storage allows the refinery to adjust its processing conditions for
different feedstocks or to adjust its product mix based on seasonal or market conditions
for an extended period of time.

Storage of finished product also occurs prior to shipment or for the purpose of
blending or additive addition. Product quality is assured and contamination or
degradation is minimised by stringent storage procedures.

Finished product tankage is therefore unlikely to be used for either intermediate

product storage or crude oil.
Crude Oil Storage - Process
Process:

Wastewater: Oily foul water, which may contain large quantities of either dissolved salts or
System suspended solids, often accumulate in tank bottoms. When this water is relatively
low in contaminants, it may be directed to an API separator for treatment. However,
when contamination is high, this water is usually sent to treatment facilities for
disposal.

A majority of waste oil and water generated throughout the refinery, will ultimately
find its path back to the waste water recovery section for treatment. There, the oily
water is converted to a suitable specification for ultimate safe discharge to the local
water course, and the oil is recovered and returned to the crude unit for processing.
Crude Oil Storage - Emulsions
Emulsions:

Crude Oil: This is the first area to treat incoming crude to a refinery, albeit via pipeline or tanker.
Storage The crude may contain significant levels of impurities left over from the oil production
treatment, or via its transportation. Pre-treatment of crude oil in the tank farm with
demulsifiers has shown to be effective in the crude oil preparation.

Recovered: Another important demulsifier application is in the refinery oil-recovery system.

Oil Usually, these systems receive many different waste oil and water (effluent) from all
parts of the refinery. In typical systems, these streams are collected and sent through
API separators to reduce the oil content. The oil emulsions that are skimmed from the
top of the API separator can be difficult to treat at times.

Tank: This operation is conducted after several years of the crude tank’s service life. It
Cleaning requires that the tank ‘bottoms’ material be removed, cleaning the tank, making any
necessary repairs and returning the tank to service.

Tank cleaning involves the use of selected demulsifiers or other surfactants. Effective
mixing/circulation, heat and settling time are essential to the success of this treatment.

Recommended Products

Problems (Corrosion)
Crude Oil Storage - Emulsions
POWERPHASE 3004
POWERPHASE 3007

PIPELINE

INTERMEDIATE CRUDE
BARGE
STORAGE STORAGE

TO CRUDE
SHIP
UNIT

RECOVERED OIL

API
SKIMMED SEPARATOR OILY
WATER
Emulsions:
OIL
Corrosion:

SLOP OIL Fouling:

SYSTEM
Foaming:
POWERCLEAR 3101
Other:
WATER & POWERCLEAR 3108
SOLIDS

Product Info
Main Menu
Crude Oil Storage - Emulsions
Crude Oil Storage - Corrosion
Corrosion:

Crude Oil: Corrosion problems and/or bacterial growth related with water separation in a crude
Storage oil tank are some of the potential problems associated with crude oil storage.
Bacterial action and corrosion (from bacterial growth) may be inhibited by the
addition of a selective biocide. Corrosion in storage tanks may be controlled by the
use of a water-soluble corrosion inhibitor.

Recommended Products

Problems (Others)
Crude Oil Storage - Corrosion
POWERCOR 2010

PIPELINE

INTERMEDIATE CRUDE
BARGE
STORAGE STORAGE

TO CRUDE
SHIP
UNIT

POWERCOR 2010
POWERCOR 2008
RECOVERED OIL

API
SKIMMED SEPARATOR OILY
OIL WATER
Emulsions:

Corrosion:
SLOP OIL
SYSTEM Fouling:

Foaming:
WATER &
SOLIDS Other:

Product Info
Crude Oil Storage - Corrosion
Crude Oil Storage - Others
Others:

Intermediate:Due to the high waxy nature of some crudes or even intermediate products, e.g. diesel,
Storage there may be at times a requirement for paraffin control or pour point depressant (PPD)
products.

Finished: In addition to intermediate products, finished products may require a chemical

Product treatment application. At times, a corrosion inhibitor / biocide may be required.
However, a more common approach would be the use of stability additives in the
finished products to prevent oxidative degradation. In a similar manner, intermediate
products may require at times the addition of stability additives.

Other products for consideration for injection into finished products would be:-

 Pour Point Depressants (PPD)

 Mid-Distillate Flow Improvers (MDFI)
 Cold Filter Plugging Point (CFPP)
 Wax Anti-Settling Additives (WASA / WAFI)
 Dehazers

The above additives ensure that the fuels meet required specifications as determined
by standard techniques.
Recommended Products
Main Menu
Crude Oil Storage - Others
POWERWAX 1007
POWERFLO 2101

POWERWAX 1007
POWERSULFA 2102
POWERBIO 2304 PIPELINE POWERBIO 2304
INTERMEDIATE CRUDE
BARGE
STORAGE STORAGE

TO CRUDE
SHIP
POWERWAX 1601 UNIT

POWERWAX 1007
POWERWAX 1007
RECOVERED OIL

POWERSCALE 1403
API
SKIMMED SEPARATOR OILY
OIL WATER
Emulsions:

Corrosion:
SLOP OIL
SYSTEM
Fouling:

Foaming:
WATER &
SOLIDS Other:

Product Info
Crude Oil Storage - Others

Recommended Approach
Crude Storage Unit – Recommended Approaches
It is difficult to recommend any one specific product for application in the
crude storage system. It depends on the actual problem that exists at that
time.

The following programs can optimise the overall crude oil storage
conditions for operations through the use of a comprehensive
Emulsions: treatment program that includes:

Corrosion: • Corrosion inhibitors to protect storage facilities against deterioration

Fouling: • Biocides to control bacterial growth in storage

• Demulsifiers to maximise removal of mineral salts, water and suspended

Foaming:
contaminants from crude oil in storage
Other: • Tank cleaners to yield maximum cleanup for the least cost

• Stability additives to prevent intermediate and final product degradation

• Demulsifiers to remove water in intermediate and final products

• Paraffin control chemicals to handle flow problems resulting from waxy crude
or intermediate streams
Next Process
 CRUDE
DISTILLATION
UNIT (CDU)

Confidential

Istiyarso
Oil and Gas Business Unit

2021
Crude Distillation Unit

Fuel Gas

Accumulator Stabiliser

Sour Water
Preflash
Column Naphtha

STM
Kerosene
STM To VAC
Diesel System
STM
Vacuum
Gas
Tower
Oil
Atmospheric
VAC Gas Emulsions:
Tower
STM Oil
Heater Corrosion:
Heater
Residuum Fouling:

Foaming:

Other:

Desalter

Crude Feed
Process

Wash Water
Potential Problems

Main Menu
Crude Distillation Unit - Process
Process:

Desalter: The crude unit consists of the atmospheric and vacuum distillation system, and all
operations necessary to prepare crude oil for processing.

Desalting is a highly effective means of removing contaminants from crude oil, which
at any one time may include chlorides and sulphates (salts) of sodium, calcium and
magnesium. Additionally, large quantities of sediment, which as well as clay, sand
can be removed. The electrostatic desalting process is a “washing process.” Crude
oil is intimately mixed with fresh water via a mix valve to ensure adequate emulsification
of the oil and water. Electrical coalescence of the emulsion within the desalter vessel
ensures complete separation of the oil and water.

CDU: Crude oil is separated in this process according to boiling point. Vacuum distillation
/VDU only differs in that the separation process is performed under vacuum.

After desalting, the crude is directed through a series of heat exchangers and its
temperature is raised to about 550oF (288oC). Further heating takes place in a furnace
(750oF/339oC) and then charged to the flash zone of the atmospheric column. The
column temperature is controlled by reflux. Steam is introduced at the bottom of the
column. A steam stripping tower allows the light-ends to be separated.

The overhead condenser condenses the C5 and heavier fraction of the vapours from the
top of the tower. This is the light gasoline portion which contains some C4’s and C5’s.

Process (Continued)
Crude Distillation Unit - Process
Process: (Continued)

CDU: Some of this condensate is returned to the tower as reflux, and the remainder is sent to
/VDU the stabiliser section of the refinery gas plant, where C4’s and C3 are separated from the
light straight-run (LSR) gasoline.

Distillation of the heavier bottoms fraction of the atmospheric tower are conducted
under vacuum, because the boiling temperature goes down as the pressure is lowered.
This process reduces the potential of thermal cracking. Vacuum distillation is carried
out with absolute pressures in the tower flash zone area of 25 to 40 mmHg.

Typical intermediate products separated during atmospheric and vacuum distillation

include butane and lighter gases, gasoline, naphtha, kerosene, gas oil and residuum.

Return
Crude Distillation Unit - Emulsion
Emulsions:

Crude Oil: This is the first area to treat incoming crude to a refinery, albeit via pipeline or tanker.
Storage The crude may contain significant levels of impurities left over from the oil production
treatment, or via its transportation. Pre-treatment of crude oil in the tank farm with
demulsifiers has shown to be effective in the crude oil preparation.

Recovered: Another important demulsifier application is in the refinery oil-recovery system.

Oil Usually, these systems receive many different waste oil and water (effluent) from all
parts of the refinery. In typical systems, these streams are collected and sent through
API separators to reduce the oil content. The oil emulsions that are skimmed from the
top of the API separator can be difficult to treat at times.

Desalter: This is normally the primary chemical program where the demulsifier [desalting aid] is
used. The demulsifier plays a central role in the overall desalting function due to the
intimate mixing and dispersion of the demulsifier and wash water into the crude oil and
the subsequent separation of the original mineral chloride-containing salts together
with the wash water. The specific operating conditions of the desalter (temperature,
electrical field intensity, mixing energy, residence time etc.) in addition with the
selection and application of the demulsifier. Changes in crude oil feedstock may
require a change in injection rate or demulsifier type.

Surfactants may be incorporated into the demulsifier to ‘water-wet’ entrained solids

and increase their affinity for the water phase.
Recommended Products
Crude Distillation Unit - Emulsion

Fuel Gas

Accumulator Stabiliser

Sour Water
Preflash
Column Naphtha

STM
Kerosene
STM To VAC
Diesel System
STM
Vacuum POWERPHASE 3004
Gas
Tower
Oil
Atmospheric
Tower VAC Gas
STM Oil
Heater
Heater
Residuum
Emulsions:
POWERPHASE 3004
Corrosion:

POWERPHASE 3007 Fouling:

Desalter
Foaming:
Crude Feed
POWERCLEAR 3108 Other:

POWERCLEAR 3101
Wash Water
Product Info
Crude Distillation Unit - Emulsion

Problems (Corrosion)
Crude Distillation Unit - Corrosion
Corrosion:

Crude Oil: Corrosion problems and/or bacterial growth related with water separation in a crude
Storage oil tank are some of the potential problems associated with crude oil storage.

Atmospheric: Corrosion in the atmospheric and vacuum distillation column is primarily controlled
/Vac Columnwith proper use of metallurgy. Corrosion in the condenser, accumulators, and other
overhead (ovhd) equipment, where water is present, is minimised by proper metallurgy
and the application of a proper chemical program.

One method to control corrosion caused by hydrochloric (HCl) and other acids is to
maintain the pH in the ovhd system between 5.5 and 6.5 by the injection of ammonia
or neutralising amines. The neutraliser is added to the ovhd vapour line or before
each bank of condensers, usually in combination with a water wash.

Dilute caustic (NaOH) can also be added to the desalted crude oil to reduce the quantity
of HCl formed. The NaOH reacts with the calcium and magnesium chlorides to form
sodium chloride, which is relatively stable at crude unit temperatures.

A comprehensive corrosion control program for overhead units also includes a

corrosion inhibitor (filming amine). The inhibitor helps provide a barrier that prevents
the corrodent from reaching the metal surface. Locations where corrosion control
programs may be necessary include the preflash tower ovhd, atmospheric tower ovhds,
pumparound system, stabiliser ovhds, and vacuum tower ovhd systems.

Recommended Products
Crude Distillation Unit - Corrosion
POWERCOR 2018 POWERCOR 2017

POWERCOR 2019

Fuel Gas

Accumulator Stabiliser
POWERCOR 2017
Sour Water
Preflash
Column Naphtha

STM
Kerosene
STM To VAC
Diesel System
STM
Vacuum
Gas
Tower
Oil
Atmospheric
Tower VAC Gas
STM Oil
Heater
Heater
Residuum
Emulsions:

Corrosion:

Fouling:
Desalter
Foaming:
Crude Feed
Other:

Wash Water
Product Info
Crude Distillation Unit - Corrosion

Product Info
Crude Distillation Unit – Fouling
Fouling:

Crude Oil: Fouling control is a major area in which chemical programs for the atmospheric and
Distillation vacuum distillation system exist. Fouling in crude preheat exchangers is most often
a result of asphaltene destabilisation. Inorganics in crude oil, such as corrosion
products or salts, contribute to crude unit preheat fouling. Fouling is controlled under
most circumstances by the addition of a fouling control aid (antifoulant), which
functions by interfering with the chemistry of fouling. For example, a stabiliser-type
antifoulant chemically stabilises asphaltenes, thus reducing their tendency to
polymerise and precipitate. In the event that corrosion products are contributing to
the fouling, an effective corrosion inhibitor can be applied.

Other areas can benefit from the application of antifoulants. These areas include
atmospheric residuum used to preheat the crude feed, reboilers in the light ends
section, and fuel gas nozzles on the crude unit furnace.

Vacuum: Fouling in the lower portions of the tower and the associated bottoms circuit may be
Unit reduced by the use of antifoulants. Deposition of contaminants such as asphaltene,
tars and other solids is minimised by the use of these products. The products may
also contain components that inhibit polymerisation or coking of the heavier fractions.

Other applications of antifoulants include the vacuum furnace feed, where coking may
occur, and the furnace fuel gas system.

Problems (Foaming/Others)
Crude Distillation Unit - Fouling

Problems (Foaming/Others)
Crude Distillation Unit – Foaming and Others

Foaming:

Crude Oil: If foaming and emulsion formation are problems in the ovhd system, antifoam and
Distillation emulsion breaker products may be added to reduce the impact of these conditions
on the operation of the unit.

Foaming may also occur if a “preflash” tower is used ahead of the atmospheric tower.

Vacuum: Parts of the vacuum tower may be subject to foaming, and antifoam products may be
Unit applied to correct this condition.

Others:

The ovhd condensate from the vacuum tower typically contains a very tight reverse
emulsion. This emulsion is usually white in appearance and can contain as much as
10% gas oil. Reverse demulsifiers have been very successful in resolving this problem.

Return
Crude Distillation Unit – Foaming and Others

Return
Check-lists
Crude/Intermed.
Furfural and
Storage
NMP Units LPG

Naphtha Reformate
Hydrotreating Reforming
Unit (HTU) Unit Gasoline

Mid Distillate Hydrodesulphuriser Kerosene, Diesel, No. 2 Fuel Oil

Crude Unit
Unit (HDS)
(Atmospheric)

Product Blending
Jet Fuel

(Oil Movement)
Hydrocracking
Atm Gas Oil Unit
Reduced Crude

Furfural and
Alkylation Alkylate Diesel
NMP Units
Unit

Lube Oil
Light Ends
Fluid Catalytic Furnace Oil
Cracking Unit
Vac Gas Oil
(FCCU) Cracked Gasoline, Lt Cycle Oil, Slurry Oil
Vacuum Unit
Asphalt No. 6 FO
Coker Gas Oil

Bottoms
Visbreaker
Unit Sour Gas Amine Sulphur Sulphur
Unit Unit

Sour Water
Stripper
Delayed Coking
Unit Coke Coke
Confidential

Istiyarso
Oil and Gas Business Unit

2021