Processes for Production of Light Olefins

( FCC Process)

College of Management & Economic Studies,

UPES, Dehradun, 11th Sept’ 2018

G.S.Dang
[email protected]
 CONTENTS

• Introduction
• FCC process & advancements
• MTO / MTP processes
• Summary
 Light Olefin Feedstocks/Production

• Light olefins ( Ethylene , Propylene ) production is from

two sources
-- From lighter feedstocks ; Ethane , Propane ,
Naphtha , Natural Gas
Process -- Steam Cracking
-- Heavier feedstocks ; Vacuum Gas Oil (VGO),
VGO + Residue
Process -- Fluid Catalytic Cracking (FCC)/
Resid FCC
 Stream Cracking of Naphtha

• It is a thermal cracking process – operates at high

temperature ( 800-850oC) on low aromatic (4 to 6 %)
naphtha, with a very short residence time e.g. 0.25
seconds in the presence of steam

• Products are light olefins ( mostly Ethylene along

with Propylene and Butylene / Butadiene) and to a
lesser extent aromatics ( BTX)

• Some liquid fractions (C5 cuts) also are obtained which can be
added to gasoline pool after hydrogenation
 Cleaning of Feed Gas ( Natural Gas )
• Typical natural gas composition ; C1 - 6 %, C2- 90 %, C3-
o.80%, C4- O.6% , C5 and others - traces

• Steam Cracker plants using natural gas have gas sweetening unit
for removal of acid gases like H2S and CO2

• Sweetened gas is then compressed and cooled to about 17oC, for

moisture separation / feed gas drying

• Gas is cooled to -60oC ; demethanization from C2/C3 at -101o C,

C2 / C3 is fed to steam cracker unit
 Steam Cracking Process

• In steam cracking, a gaseous or liquid feed is diluted

with steam and heated in a furnace without the
presence of oxygen

• Reaction temperature is very high ( around 850°C)

but with very low residence time

• In modern cracking furnaces, the residence time is

in milliseconds to improve yield
 Steam Cracking Sections

• Steam cracking section comprises a hot section and a

cold section

• Cracking of hydrocarbons and separation of cracked

light gases from heavier fraction pyrolysis gasoline
takes place in the hot section

• Separation of light cracked gases Ethylene , Propylene

Butylene and other fractions takes place in cold section
operating below zero deg centigrade
 Steam Cracking Furnace

Typical Single Cell Gas Cracking Furnace – 220000 Tonnes / annum

Single Cell Liquid Cracking Furnace - 170000Tonnes / annum
 Steam Cracking Plant - Capacities

• Average capacity -- 50,000 t/y ethylene in

1950s

• Current capacity -- 450,000 t/y

• No of plants in the world -- about 300

 Light Olefins- Major Production Processes

For most processes, ethylene is the main output product,

followed by propylene

Other major processes for producing of olefins;

• Olefins from FCC Process (Recovery from off gasses)

• Methanol to olefin (MTO) / Methanol to propylene (MTP)
Refinery Flow Diagram

(FCC UNIT)
 Olefins recovery from FCC off gasses

• FCC ( Fluidized Catalytic Cracking) process is an

important cracking process in a refinery

• It converts Vacuum Gas oil ( VGO) boiling range 370-

540oC into lighter fractions ; generates major
component for gasoline blending

• Light olefins particularly propylene are also

produced / separated from off gases of the unit
 Olefins from FCC Process
• In the FCC process more of propylene is produced by
cracking

• The reaction proceeds readily over ZSM-5 zeolite-

containing catalyst

• Through technological developments in FCC process

the yield of Propylene is increased from about 7 % to
around 20%
 FCC Block Diagram

CO,CO2,H20
GASES
OLEFINIC & LPG

OR
R LIGHTER
REACTOR

RAT
A DISTILLATES
C

ENE
Feed TI
O
LCO
REG
N
A
T CLARIFIED OIL
CATALYST O
R
RECYCLE
AIR

14
 FCC Process Flow Diagram

Reactor

Regenerator

Feedstock

*Catalyst

* Catalyst circulates between Reactor and regenerator

FCC Reactor & Regenerator

• Flue gas temperature 600 to 760OC

• Heat Recovery from flue gas for stream

generation
 FCC Process Details
Purpose : Converts heavy oils into gasoline and/ or light olefins
Licensors Axens (IFP) ExxonMobil
KBR Stone & Webster
UOP
Catalyst and Additives
Zeolites (highly acidic, catalyzes cracking)
Rare-earth oxide (increase catalyst stability)
ZSM-5 (increase octane and production of light olefins)
Pt (promotes combustion of CO to CO2 in regenerator)
Feeds Atmospheric gas oil Vacuum gas oil
Coker gas oil Deasphalted oil
Lube extracts Vacuum Resid (up to 20 vol%)
Typical Feed Properties
Nitrogen <3000 wppm
Carbon residue <5.0 wt%
Nickel + Vanadium <50 wppm
90% boiling point <1300 oF (705oC)
Typical Process Conditions
Feed temperature 300 – 700 oF (150-370oC)
Reactor temperature 920 – 1020 F (495-550oC)
o

Regenerator temperature 1200 – 1350 oF (650-730oC)

Catalyst/ Oil ratio 4.0 – 10.0
Reactor pressure (170 – 343 KPa)
Typical Product Yield
Conversion 70 -84 vol%
H2, H2S methane, ethane 3.0 -3.5 wt%
Propane and propylene 4.5 – 6.5 wt%
Butane and butenes 9 -12 wt%
Gasoline 44 - 56 wt%
LCO 13 – 20 wt%
Slurry Oil 4 – 12 wt%
Coke 5 – 6 wt%
18
 New Technologies for Propylene

Deep Catalytic Cracking (DCC)

• A high severity FCC process

• Fluidized catalytic cracking process using a proprietary

catalyst for selective cracking of a wide variety of heavy
feedstocks to give light olefins in higher quantities

• The process, developed by RIPP of SINOPEC, has been

commercially proven with seven units built since 1990,
six in China and one in Thailand
 New Technologies for Propylene
SUPERFLEX

• The SUPERFLEX process is a proprietary technology exclusively

offered for license by Kellogg Brown & Root

• It uses an FCC system with a proprietary catalyst to convert low-

value feedstock with high olefin content to petrochemical
products such as propylene and ethylene

• The feedstock can be olefin-rich light hydrocarbons in the carbon

range C4 to C8, and the ideal feedstocks are C4 and C5 streams
generated in the steam cracker
 New Technologies for Olefins

• Due to shortfall in light fraction supply as feedstock,

integration of a steam cracker with FCC modified
processes such as DCC , SUPERPLEX etc is generally
the best choice

• Such a combination means making full use of non-

catalytic with a catalytic process
 Propylene Production .. Contd.

New and novel lower-cost chemical processes for propylene

production are

• Methanol-to-Olefins/Methanol-to-Propylene (MTO/MTP),
• Propane Dehydrogenation (PDH),

Among various olefin production processes MTO/MTP and PDH

stand out due to the use of low-cost raw materials
 MTO /MTP ( Methanol to Olefins / Propylene)
• Production of olefins via the methanol to olefins (MTO) such as
UOP/Hydro, Lurgi and Exxon Mobil is also developed / commercialized

• These processes allow the cost-effective production of methanol and

the olefins

• MTP process ensures the conversion of this product into high-grade

propylene

• Air Liquide is putting up a 500,000 ton/y methanol-to-propylene

(MTP) plant ( Lurgi technology) for Shenhua Ningxia Coal Industry
Group (SNCG; China) at Ningdong , in Nangxia province
 Methanol to Olefin ( MTO) Process

The UOP/HYDRO MTO process converts methanol to light

olefins. The process provides greater selectivity to
ethylene and propylene versus C4+ by products.
The MTO reaction scheme :

Ethylene

Mol. Sieve Catalyst

Methanol Propylene

Butylene
Other by products : H2O, H2, CO2,
C1-C5 , Paraffins , C5+ Coke
 MTO Process

• Availability of low cost of methanol is the basis of the process

• The ethylene and propylene are produced from a

dimethylether (DME) intermediate in the MTO process

• Some by-products such as butenes and other higher olefins are

also produced

• The MTO reaction is exothermic. The coke deposited on the

catalyst is removed by combustion with air in a catalyst
regenerator system in order to prolong the active life of the
catalyst
 MTO Process
• Reaction occurs in the vapour phase at temperatures between
350 and 600 °C, and pressures between 0.1 and 0.3 MPa and
Residence times are very short

• The results from an MTO demonstration plant show that the

conversion of methanol is 100 %, selectivity to ethylene is above
40 %, and selectivity to propylene is close to 40 %
 Methanol to Propylene (MTP)

• MTP process, developed by Lurgi, depending

on the reaction conditions and operating
parameters used produces:
 Propylene as main product,
 Ethylene and other olefins,
 Fuel gas, gasoline range hydrocarbons, and
 Liquefied petroleum gas
 Methanol to Propylene (MTP)

• MTP process, developed by Lurgi, operates at atmospheric

or nearly atmospheric pressure at a reaction temperature
range of 350–500 °C using a fixed bed reactor and ZSM‐5
zeolite catalyst

• Propylene selectivity achieved is about 35% in one‐pass

• Commercial use of the MTP process involves fixed‐bed

reactors, obtaining higher selectivity by recycling the
formed olefins, after Propylene extraction, into the reactor
 Methanol to Propylene (MTP)

• A fully integrated polypropylene complex including

 methanol-to-propylene processing unit,
 a methanol production unit (natural gas to
methanol) and also
 a 450,000t/yr polypropylene production plant went
on stream in late 2012
( at Trinidad and Tobago by the NGC and NEC)
 Methanol to Propylene (MTP)

• A Methanol-to-olefins (MTO) unit, technology provided by

Honeywell UOP, at Jiangsu Sailboat Petrochemical Company, Ltd
has started operation recently in 2017

• With a production capacity of 833,000 metric tons per year, the

unit is the largest single-train MTO unit in the world

• The new plant converts methanol from domestic coal into

olefins for plastics production

(World’s largest single-train methanol-to-olefins plant)

 Propane Dehydrogenation (PDH)

• Propane dehydrogenation (PDH) is used to produce polymer-

grade Propylene from Propane independent of a steam cracker
or fluid catalytic cracking unit

• It provides a dedicated / reliable source of Propylene to meet

the growing market demand for Propylene and gives more
control over propylene feedstock costs
 Propane Dehydrogenation (PDH)

• UOP C3 Oleflex Process Propane Dehydrogenation makes

propylene
C3H8 >>> C3H6 + H2

• Propane dehydrogenation is achieved over vanadium oxide

catalysts at 475°C - 550°C

• Used commercially where Propylene is in short supply as in

Middle East and Far East ; Polymer grade Propylene is produced

• PDH provides the lowest cost of production and highest return

on investment
 Propane Dehydrogenation (PDH)

• A PDH unit with a capacity of 750,000 mt/year started

operations in Mont Belvieu, Texas, US in June 2018,
reaching full capacity

• The unit was initially slated to start up at the end of

2016, but due to repeated production issues and
Hurricane effect it got delayed
 MTO/MTP

Technology Advancement
• 2.6 tonnes of Methanol is needed to produce
1 tonne of olefin in second generation
technology as against 3.0 tonnes of Methanol
in first generation technologies
 Summary
• Steam cracking has been the major source of light
olefins
• Naphtha is currently the dominant feedstock,
accounting for 50~55% of the total
• Ethane, associate gas and condensates are gradually
replacing naphtha as the major feedstock because
these are easier to obtain at a lower price
• In North America and the Middle East, ethane and
associate gas already make up 25~40% of the
feedstock for steam cracking
 Summary

• Other major processes include FCC and its advance

versions, MTO / MTP

• Also PDH is being adopted widely

37
Refinery off-Gas Cracker (World's largest ) at Jamnagar
RELIANCE INDUSTRIES LIMITED

• World's largest refinery off-gas cracker(ROGC)

commissioned at Jamnagar in late 2017

• Refinery off-gas cracker (ROGC) complex of 1.5 million

tonnes per annum (MTPA) capacity along with
downstream plants and utilities

• ROGC complex is at its integrated Refinery-

Petrochemicals complex at Jamnagar
 Vertical integration across the Value Chain

• The ROGC complex has a unique configuration as it uses off-gases from RIL's
two refineries at Jamnagar as feedstock

• This innovative approach provides a sustainable cost advantage, making ROGC

competitive with respect to the crackers in Middle-East and North America
which have feedstock cost advantage

• ROGC is the latest addition to RIL's existing crackers , consisting of cracker

facilities at Nagothane in Maharashtra and Hazira, Dahej and Vadodara in
Gujarat

• There are nearly 270 ethylene plants globally with a combined capacity of over
170 MTPA. RIL's combined ethylene capacity is now close to 4 MTPA at five of
its manufacturing sites. With ROGC and imported ethane, RIL has one of the
most competitive and flexible cracker
 ROGC
• Ethylene from ROGC is used in downstream plants to produce
Mono-Ethylene Glycol (MEG) and Polyethylene (LLDPE and LDPE)

• Propylene from ROGC has enhanced output of the existing

Polypropylene (PP) plants at Jamnagar complex to produce high-
value co-polymers

• The commissioning of MEG plant marks completion of all-round

expansion of the polyester value chain post successful
commissioning of para-xylene (PX), Purified Terephthalic Acid
(PTA), Polyester Filament and Poly Ethylene Terephthalate (PET)
plants over last three years
 The ROGC complex has a unique configuration as it uses
off-gases from RIL’s two refineries at Jamnagar as feedstock