NAPHTHA AND GAS CRACKING FOR

PRODUCTION OF OLEFINS

Olefins: ethylene and propylene

The largest volume petrochemicals produced in

which Annually global production of ethylene is

about 120 million tons with a continuous annual
increase of some 4 - 5 %.
Ethylene and propylene have no end use, they are
building blocks for a large variety of chemicals and
petrochemical products.
Polymers are the dominating end-users.

 Olefins are major building blocks for petrochemicals. Because

of their reactivity and versatility, olefins especially the light

olefins like ethylene, propylene, butenes, butadiene, etc., there
has been tremendous growth in the demand of the olefins.
Olefins are finding wide application in the manufacture of
polymers, chemical intermediates, and synthetic rubber.
Ethylene itself is basic building block for large number of
petrochemicals and is quoted as king of chemicals.
Some of ethylene manufacturing company and their capacity is
given in Table M-VII 2.1.
The global ethylene capacity at January 1, 2011, net additions
and closings was more than 138 million tones compared with
nearly 130 million tones in 2008 [Oil & gas J. Vol 129, 2011].
Global ethylene capacity is given in Table M-VII 2.2.

STEAM CRACKING FOR PRODUCTION OF OLEFINS

The steam cracker remains the fundamental unit and is the heart

of any petrochemical complex and mother plant and produces

large number of products and byproducts such as olefins
ethylene, propylene, butadiene, butane and butenes, isoprene,
etc., and pyrolysis gasoline.
The choice of the feedstock for olefin production depends on the
availability of raw materials and the range of downstream
products.
Naphtha has made up about 50-55percent of ethylene feedstock
sources since 1992. Although basic steam cracking technology
remain same for naphtha, gas oil and natural gas, different
configuration of steam cracking plant are available from various
process licensors [Petrochemical processes, 2003].

Steam cracking challenges

The steam cracking process has high yields with

high temperature in the cracking furnaces.

Steam cracking furnace valves play an important
role in ensuring proper ethylene process
performance.
Reliable and accurate control, on-off and valve
performance is vital during normal production and
frequent furnace decoking operations to ensure
total process productivity and safety.

 The indicated feedstock's (ethane, propane, butane, naphtha

and gas oil) are fed to a pyrolysis (steam cracking) furnace,

where they are combined with steam and heated to
temperatures between approximately 1450 - 1600 F (790 870 C). Within this temperature range, the feedstock
molecules "crack" to produce ethylene as well as methane,
hydrogen, ethylene, propylene, butadiene, benzene, toluene
and other co-products.
After the pyrolysis reaction is quenched, the rest of the
plant separates the desired products into streams that meet
the various product specifications.
Process steps include distillation, compression, process gas
drying, hydrogenation (of acetylenes), and heat transfer.

Hot Section:
The cracker furnace may be divided into three sections:

convection zones, radiation zones and quench section.

The hydrocarbon feed stock is preheated by quench water and
steam before entering the convection zone of the furnace where
it is further preheated and mixed with superheated steam, which
is added as a diluent.
The steam minimizes the side reaction responsible for the
formation of coke during pyrolysis and improves the selectivity
to produce desired olefins by lowering hydrocarbon partial
pressure.
The requirement of steam will depend upon the type of
feedstock; the lighter hydrocarbon requires less steam as
compared to heavier feedstock.

 The hydrocarbon and steam preheated in convection zone in the

upper part of the furnace enter the radiant section of furnace at

about 6500C & total pressure of 1.7 bar, where pyrolysis of feed
takes place.
The coil length in the radiant section varies from 60m for a
naphtha cracker to 85m for an ethane cracking unit.
The resistance time varies for different feedstock is around 0.151.2 sec and Reynolds number is around 3,00,000.
The effluent leaves at a temperature of 830-8700C and Pressure of
1.7 bar.
The flue gas temperature may be of the order of 12000C with the
inner tube skin temperature of 10080C.
The reaction is endothermic. Here heat flux ranges from 5585kJ/m2.
The radiant coil outlet temperature is controlled to achieve desired
ethylene and propylene yield.

 Pyrolysis of any hydrocarbon feedstock is always accompanied

by coke formation, which deposits on the walls of the reactor

under typical operating conditions.
the furnace effluent is rapidly quenched in double pipe heat
exchangers and multi-tubular heat exchangers which cools to at
a temperature of 3500C.
The effluent is further quenched by direct contact with quench
oil before entering the quench oil tower where besides cooling
the furnace effluent, the separation of gasoline and lighter
products from fuel oil also takes place.
here quenching is essential in order to restrict the
polymerization reactions.
Ethylene cracking effluent must be quenched uniformly and
rapidly for high product yield.

 Quenching is performed in two ways directly by oil or

water (OR) Indirectly by a quench cooler.

The basic requirements for cracked product quench
coolers are rapid and uniform cooling, small pressure
drop, maximum heat recovery, long continuous run
length and low maintenance.
The cracked gas overhead of the quench oil tower is
further cooled in the quench water tower by direct
contact with water and is finally sent to primary
fraction column.
The gases are separated at the top and are sent to
compression section for separation and purification of
cracked products.

17

A greener chemistry

18

A greener chemistry

Cracked gas compression and dehydration:

The effluent from primary fraction column is compressed in four or
five stages on centrifugal compressor containing intercoolers and then
to a separator drum.
The condensate from separator drum enters a stripper where the
higher fractions are recovered.
The gas before entering the final stage compression is desulfurized by
passing through a caustic scrubber where the separation of sulphur
compounds and CO2 takes place.
The removal of CO2 from gas is essential in order to meet the product
quality.
The removal of CO2 also avoids corrosion and formation of CO2 ice
in the cold section.
The cracked gases are dried in dehydrators containing molecular sieves
before entering the cold section.

Cold section:
The dried cracked gas after removal of sulphur
compounds, CO2 and moisture are sent to cold section
where it is cooled to -1650C in cascade refrigeration
system using propylene and ethylene.
The cold section contains demethanizer, deethanizer,
acetylene hydrogenation unit, ethylene separation,
depropanizer, C3 hydrogenation and debutanizer.
Here refrigeration system is an important part of any
ethylene plant.
The recovery of ethylene will depend on reliability and
flexibility of the system, as a coolant at different
temperature levels.

Demethanizer:
The cracked gases after cooling to -1650C are sent to

demethanizer which operates at a pressure of about 7 atm

in case of low pressure demethanizer or 355 atm in case of
high pressure demethanizer.
The purpose of demethanizer is to make sharp separation
between methane and ethylene.
Demethanizer operating performance is very much
dependent on its feed condition, temperature, pressure and
flow rates.
Demethanizer operation is most sensitive to flow rates and
temperature and least sensitive to pressure.

Deethanizer:
The demethanizer bottom portion consisting of ethylene and heavier
fraction is sent to deethanizer which is essentially as fractionator
operating pressure of about of 24 kg/cm2 and temperature -100C.
The deethanizer separates the demethanizer bottom into C2 overhead
and C3 sent to depropanizer for separation of propane.
Acetylene hydrogenation Unit:
the deethanizer overhead is sent to acetylene hydrogenation system
where acetylene is catalytically hydrogenated to ethane and ethylene in
the presence of palladium catalyst at a temperature of 400C & 3 atm
pressure.
the removal of acetylene is important because of its presence during
ethylene polymerization gives a polymer containing double bonds,
which is cross linked to give a non-linear product.

Ethylene separation:
the acetylene free effluent is cooled and sent to ethylene ethane
separator, which is essentially a distillation where ethylene is
separated in the column which operates at -350C and 20 kg/cm2.
Depropanizer:
The bottom of the deethanizer containing C3 and higher fractions
are sent to depropanizer column where separation between C3
and C4 compounds are achieved.
C3 Hydrogenation:
The C3 cut at the top of the propanizer is sent to C3
Hydrogenation unit where methyl acetylene and propadiene are
catalytically converted to propylene and propane in a liquid phase
reactor in presence of hydrogen before carrying out separation of
propylene.

Debutanizer:
The bottom portion from the depropanizer is sent to
debutanizer, which produces a butadiene rich, C4 cut at the top.
The bottom stream, which is essentially pyrolysis gasoline is sent
to pyrolysis gasoline processing unit for separation of aromatics.
Pyrolysis gasoline fractionator:
Feed to the gasoline fractionator is from the bottom portion of
the debutanizer. Here the gasoline is separated from the wash oil
and heavier fraction.
Fuel oil stripper:
fuel oil stripper separates wash oil from heavier fuel oil
components.

Olefins complex: a steam-cracking unit

Hydrogen
Utilities
Material Movements

Mixed
Butanes
Gasoline

Acid Gas
Compressor and
Drier Chilling

Steam
Primary
Fractionator
Quench

Feeds

NAPD
Converter

Propylene
Propane

Ethylene
Mixed
Products

Acetylene
Converter

Ethane

Ethane

Methane

Quench

Fuel Oil
Cracking
Furnaces

A greener chemistry

Naphtha

27

OPERATING VARIABLES IN STEAM CRACKING

Some of the operating variables which affects the performance of

steam crackers are: type of feedstock, reaction temperature,

pressure, steam to hydrocarbon ratio and outlet pressure.
Type of feed stock:
The various feed stocks for steam cracking are naphtha, natural
gas liquid and gas oil.
The yield of the ethylene varies depending upon the type of feed
stock used.
Ratio of ethylene and propylene yields decreases steadily from
ethane to the heavier fractions like naphtha and gas oil, while the
pyrolysis gasoline yield increases with the increase in the
hydrocarbon heaviness.
Here pyrolysis gasoline is an important source of aromatics.

Pyrolysis temperature and Residence Time

The effluent gas exit temperature is generally considered a

significant indicator of the operation of a furnace.

As the furnace exit temperature rises, the yield also rises, while
the yields of propylene and pyrolysis gasoline (C5-200oC at)
decrease. With respect of ethylene yield, each furnace exit
temperature, correspond to an optimum.
The highest ethylene are achieved by operating at high severely,
namely, around 850oC with residence time ranging from 0.2 to
0.4s However, operating at high temperature results in high coke
formation.

Partial Pressure of Hydrocarbon & Steam to Naphtha Ratio

Pyrolysis reaction producing light olefins are more advanced at lower

pressure. Decrease into the partial pressure of hydrocarbons by

dilution with steam, reduces the overall rate reaction rate, but also
help to enhance the selectivity of pyrolysis substantially in favor of the
light olefins desired.
Other role of steam during pyrolysis is
(1) to increase the temperature of feed stock
(2) reduction in the quantity of heat to be furnished per linear
meter of tube in the reaction section
(3) to remove partially coke deposits in furnace tubes.
The ethylene yield decreases as the partial pressure of hydrocarbon
increases. The effect of H2O/naphtha on ethylene yield is gives the
economic reason a value of 0.5 to 0.64 of steam per ton of naphtha.
Steam to hydrocarbon weight ratios range between 0.21 for ethane
and approximately 11.2 for liquid feeds.

Severity and Selectivity

Severity is often used to describe the depth of cracking or extent of

conversion.
The definition of severity varies with the different manufactures and
may differ accordingly to the type of hydrocarbon treated.
In the case of steam cracking of the ethane and propane, it is
convenient to express the severity of the operating conditions in
terms of feed conversion.
At very high severities, the methane and ethylene yield level off,
while those of propylene and C4 cut reach a peak and then decline
consequently.
The ratio of ethylene and propylene yield increases with severity,
which hence favors the formation of ethylene. The relative
production of C5+ cut passes through a minimum and at the very
high severity tends to increase.
Modern ethylene plants are normally designed for near maximum
cracking severity because of economic considerations.

Furnace Run Length

Furnace run length can be calculated from the equation

Coke formation, decoking

During steam cracking of hydrocarbons, coke is formed due

to undesired side reactions involving unsaturated molecules

and aromatic nuclei.
Due to coke deposit, the surface temperature of coil is
increased which effects the service life of coil;
Pressure drop is increased due to reduction in the inner
diameter of the coil upon coking;
Corrosion of the coil also occurs;
Reduces the product yield,
Increases the energy consumption;

At present three mechanisms have been proposed to

account for coke formation in hydrocarbon pyrolysis:
Coke formation via surface catalyzed reactions due to
carbides.
Coke formation via polycyclic aromatic hydrocarbons
in the gas phase
Coke formation directly through the reactions of small
gas phase species e.g. acetylene, butadiene and free
radicals such as methyl, ethyl, vinyl, phenyl and benzyl
radicals.

If coke is formed inside the tube reduces the heat

transfer area; increase the pressure drop, which

affects the ethylene production due to higher inlet
pressure.
The coke formation inside the will depend upon:
Characteristics of feed stock;
Hydrocarbon partial pressure
Thermal condition of coil
Feed flow rates

Some of the techniques used for reducing coke formation:

pretreatment of feedstock
Material of construction of reactor
Addition of coke inhibitors such as antimony, copper,
phosphorous and chromium etc.,
catalytic gasification of coke to form CO and hydrogen
Coating and surface enrichment using Mg, Si, Al, Cr, etc.,
Increasing steam dilution
pretreatment of inner surface of coil.

Thermal cracking furnace design

Pyrolysis furnace design during the last three decades made significant

development.
Prior to 1960, the ethylene pyrolysis furnaces were box type with
horizontal radiant tubes. The capacity of these furnaces were small
capacity (40 MM lb/y) today standards (250 MMlb/y).
High thermal efficiency furnace design can contribute greatly to
minimum overall plant utility costs.
Higher efficiency can be achieved by
Upgrading of pyrolysis furnace capacity
Increasing cracking severity

Improving ethylene selectivity

Improving thermal efficiency
Reducing downtime for decoking
Reducing maintenance cost.

 This can be achieved by radiant coil with shorter

residence time and lower pressure drop,

combustion air preheating and short residence time.
Small diameter coils coupled with increased
dilution steam, with use of booster compressors to
reduce furnace outlet pressure can increase
efficiency ethylene selectivity.
Radiant coils with a short residence time and low
hydrocarbon partial pressure give higher ethylene
selectivity.

Various technological developments for steam

crackers have been incorporated with basic objective
to have:
lower energy consumption per ton of ethylene
improved overall yield of ethylene by short
residence time and high severity.
total feed stock flexibility, gas to liquid
higher furnace availability
increase furnace tube life
reduced the maintenance cost

Gas sweetening unit

Steam cracker plants using natural gas as feedstock contain

gas-sweentening unit.
It can be defined as removal of acid gases like H2S and CO2
present in the natural gas.
the composition of natural gas before sending into the
sweetening unit:
Component

Percentage

C1

84.06

C2

9.38

C3

0.99

C4

0.04

CO2

5.52

H2S

4 ppm

N2

0.01

 Natural gas contains C02 and H2S and this gas is fed to a C2-C3

recovery unit for cryogenic separation.

If CO2 component of the gas is not removed it will freeze(770C) resulting in the choking the pipelines.
Some of the process technologies available for separation of CO2
are amine sweetening using MEA,DEA process and membrane
process.
However, amine sweetening process is most commonly used and
CO2 removed by absorption in two parallel high pressure
absorbers.
The gas is fed to two absorber columns at 52 kg/cm2 and 300C
operating in parallel.
the raw gas is taken into raw gas drum for separation of any
moisture present in the gas before passing to the absorber.

 Each absorber is fitted with valve trays. Lean diethanolamine

solution is fed to column top at tray-2 at 51.4 kg/cm2 and 450C.

The gas is counter currently contacted with the absorbent DEA
so that CO2 in the gas gets absorbed into the solution.
CO2 in the gas reacts with amine to form amine carbamate.
CO2 + 2R2NH R2NCOO- + R2NH2+
CO2 also reacts with water and hydroxyl ions to form carbonic
acid and bicarbonate ions.
CO2 + H2O H2CO3
CO2 + OH- HCO3The carbonic acid reacts with amine to form amine bicarbonate
(HCO3 & R2NH2) and amine carbonate(CO3(R2NH2)2)

the treated gas leaves form the column top at 450C and it
contains <50ppm of CO2.
The treated gas from both the columns is combined and sent to
the water wash column.
Lean amine temperature is to kept 10-150C higher than the feed
gas temperature so as to prevent heavier component in the feed
gas from condensing.
After CO2 absorption, the rich amine is collected at the bottom
of each column. This solution at 52kg/cm2 and a temperature of
720C is routed to the amine recovery unit for separation of CO2
where first sent to amine flash drum for separation of
hydrocarbons.
The rich amine solution is then sent to regenerator for stripping
of CO2 after preheating to 1100C, which is passed through a
series of filters for removal of solid scales, dissolved
hydrocarbons. Which can promote corrosion and foaming
problems.

 After CO2 absorption the treated gas is fed into the bottom of

sweet gas wash water column where the gas is counter-currently

contacted with circulating water to remove any DEA solution
carried over with the treated gas.
The treated gas after cooling is sent to the C2/C3 recovery
section for extraction of C2/C3 component.

C2/C3 Extraction unit

The sweetened gas from gas sweetening unit is fed to the

feedstock drum for separation of any entrapped liquid form the

feed gas and then it is compressed and cooled to 170C.
It is then sent to feed gas moisture separator and feed gas drying
section for removal of traces of moisture.
The gases after passing through filter are sent through series of
exchangers for cooling to below -600C and then sent to the cold
section.
in the cold section the gases are sent to demethanizer column for
separation of methane form the C2/C3.
The temperature in this column maintained is about -1010C

Alpha olefins

Alpha Olefins
Application:
To produce high-purity alpha olefins (C4 C10)
suitable as copolymers for LLDPE production and
as precursors for plasticizer alcohols .
Production of polyalphaolefins using the Alpha
Select process.
This process is simple;
It operates at mild operating temperatures and
pressures and only carbon steel equipment is
required.
The catalyst is nontoxic and easily handled.

(1). Liquid-phase Reactor

(3). Distillation column

(2). Catalyst separator

(4). Fractionation column

Linear

 Polymer-grade ethylene is oligomerized in the liquid-

phase reactor (1) with a catalyst/solvent system designed

for high activity and selectivity. Liquid effluent and
spent catalyst are then separated (2); the liquid is distilled
(3) for recycling unreacted ethylene to the reactor, then
fractionated (4) into high-purity alpha-olefins. Spent
catalyst is treated to remove volatile hydrocarbons and
recovered.
The table below illustrates the superior purities
attainable (wt%) with the Alpha-Select process:
Component

Purity

n-Butene-1

>99%

n-Hexene-1

>98%

n-Octene-1

>96%

n-Decene-1

>92%

 Yields: Yields are adjustable to meet market requirements and

very little high boiling polymer is produced as illustrated:

Alpha-olefin product distribution, wt%
Component

Yield (wt%)

n-Butene-1

33-43

n-Hexene-1

30-32

n-Octene-1

17-21

n-Decene-1

9-14

In particular, the Alphabutol process for producing

butene-1 for which there are 19 units producing 312,000

tpy.

Licensor: Axens, Axens NA.

 The -Sablin process produces -olefins such as butene-1,

hexane-1, octene-1 decene-1, etc. from ethylene in a

homogenous catalytic reaction.
The process is based on a highly active bi-functional catalyst
system operating at mild reaction conditions with highest
selectivities to -olefins.
Ethylene is compressed (6) and introduced to a bubble-column
type reactor (1) in which a homogenous catalyst system is
introduced together with a solvent.
The gaseous products leaving the reactor overhead are cooled in
a cooler (2) and cooled in a gas-liquid separator for reflux (3)
and further cooled (4) and separated in a second gas-liquid
separator (5).

 Unreacted ethylene from the separator (5) is recycled via a

compressor (6) and a heat exchanger (7) together with ethylene

makeup to the reactor.
A liquid stream is withdrawn from the reactor (1) containing liquid
-olefins and catalyst, which is removed by the catalyst removal unit
(8).
The liquid stream from the catalyst removal unit (8) is combined
with the liquid stream from the primary separation (5).
These combined liquid streams are routed to a separation section in
which, via a series of columns (9), the -olefins are separated into the
individual components.
By varying the catalyst components ratio, the product mixture can be
adjusted from light products (butene-1, hexene-1, octene-1, decene-1)
to heavier products (C12 to C20 -olefins). Typical yield for light
olefins is over 85 wt% with high purities that allow typical product
applications.
One plant of 150,000 metric tpy capacity is currently under
construction for Jubail United in Al-Jubail, Saudi Arabia.

(1). Bubble column type Reactor

(2). Cooler (3). Gas- liquid separator
(4). Cooler
(5). Unreacted ethylene separator
(6). Compressor
(7). Heat exchanger (8). Catalyst removal unit
(9). Series of distillation columns

Production of alpha olefins by Thermal cracking

wax
Thermal cracking of wax is carried out in a tubular furnace at 500-

6000C for 5-15 sec.

The products are separated from primary fractionation column and
stabilization column.
Mild condition is used to maximize the yield of alpha-olefins.
Ethylene,
Propylene

Purification

Vaporizer and
Preheater

Fractionator

Wax

C4-C18
alpha Olefins
C20 +

Shell Higher Olefins Process

Basic info on the SHOP
Oligomerization The process of converting a monomer or a
mixture of monomers into an oligomer (consists of limitted no of
monomers)
Isomerization rearrangement reaction that occurs when

compounds with the same formula exhibit different structures (e.g.

1 butene and 2 butene)

Metathesis catalytic reaction in which alkenes are converted into

new products by breaking - up and reformation of C-C double

bonds.

Metathesis of C4 C8 and C16 C40 internal olefins

Short and long chain internal olefins disproportionate

CH3CH=CHCH3 + CH3(CH2)8CH=CH(CH2)8CH3 2 CH3CH=CH(CH2)8CH3

C4 Internal olefin
C20 internal olefin
C12 internal olefin

Product profile of alpha olefins

C4 alpha olefins: LLDPE, MA, MEK,Butene-1 Plastics, solvents,

etc.,
C4-C8: Comononers for LLDPE, HDPE,C9 Oxo-alcohols, C10
olefins Plastics, plasticizers and detergents etc.,
C6-C12 Improved flexible PVC
C8-C12 : Mercaptans and rubber chemicals chain transfer agents,
oxo-alcohols etc.,
C10-C16 Detergents etc.,
C14-C18: Alpha olefin sulphonates household and industrial
detergents and toilet soaps etc.,
C20-C24: Chlorinated paraffins, polybutenes plasticizers and
leather tanning etc.,
C24+ : Waxes and emulsions Candles, coating papers and textile
processing

Olefinsbutenes extractive distillation

Application:
Separation of pure C4 olefins from olefinic/paraffinic C4 mixtures
via extractive distillation using a selective solvent.
BUTENEX is the Uhde technology to separate light olefins from
various C4 feed stocks, which include ethylene cracker and FCC
sources.
Description:
In the extractive distillation (ED) process, a single-compound
solvent, N-Formylmorpholine (NFM), or NFM in a mixture with
further morpholine derivatives, alters the vapor pressure of the
components being separated.
The vapor pressure of the olefins is lowered more than that of the
less soluble paraffins.
Paraffinic vapors leave the top of the ED column, and solvent with
olefins leaves the bottom of the ED column.

 The bottom product of the ED column is fed to the

stripper to separate pure olefins (mixtures) from the

solvent. After intensive heat exchange, the lean
solvent is recycled to the ED column.
The solvent, which can be either NFM or a mixture
including NFM, perfectly satisfies the solvent
properties needed for this process, including high
selectivity, thermal stability and a suitable boiling
point.
Two commercial plants for the recovery of n

butenes have been installed since 1998.

Olefinsbutenes extractive distillation

Olefins conversion technology

OCT converts normal butylenes and

ethylene to polymer grade propylene via

metathesis.
The two main equilibrium reactions taking
place are metathesis and isomerisation.
Propylene is formed by the metathesis of
ethylene and butene-2, and butene-1 is
isomerised to butene-2 as butene-2 is
consumed in the metathesis reaction.

 Fresh C4s (plus C4 recycle) are mixed with ethylene

feed (plus recycle ethylene) and sent through a guard

bed to remove trace impurities from the mixed feed.
The feed is heated prior to entering the vapour phase
fixed-bed metathesis reactor where the equilibrium
reaction takes place.
The catalyst promotes the reaction of ethylene and
butene-2 to form propylene and simultaneously
isomerises butene-1 to butene-2.
The per-pass conversion of butylene is greater than 60
per cent, with overall selectivity to propylene
exceeding 90 per cent.
The product from the metathesis reactor is primarily
propylene and unreacted feed.

 Reactor effluent is sent to the ethylene recovery tower where

the unreacted ethylene is recovered and recycled to the

reactor.
The C2 tower bottoms is processed in the C3 tower to produce

propylene product and a C4 recycle stream. Purge streams

containing non-reactive light material and C4s and heavier are

also produced.
Depending on the quantity of isobutylene in the C4 feed, the

unit design may include a deisobutaniser to extend reactor

run-length OCT process flow schematic between regenerations
and reduce OCT unit throughput, resulting in an overall lower
capital cost plant.

MTO PROCESS
Application:
To produce ethylene, propylene and butenes from natural gas or
equivalent, via methanol, using Hydro MTO (methanol to olefins)
process.
Description:
This process consists of a reactor section, a continuous catalyst
regeneration section and product recovery section. One or more
fluidized-bed reactors (1) are used with continuous catalyst transfer
to and from the continuous catalyst regenerator (2).
The robust regenerable MTO-100 catalyst is based on a nonzeolitic
molecular sieve. Raw (nondewatered) methanol is fed to the lowpressure reactor (1), which offers very high (99%+) conversion of
the methanol with very high selectivity to ethylene and propylene.

 The recovery section design depends on product use, but will

contain a product water recovery and recycle system (3), a CO2

removal system (4), a dryer (5), a deethanizer (6), an acetylene
saturation unit (7), a demethanizer (8), and a depropanizer (9).
The process can produce polymer-grade ethylene and propylene
by adding simple fractionation to the recovery section.
The process gives very high total olefins yields. Ethylene to
propylene product weight ratio can be modified between the
range of 0.75 to 1.3 by altering reactor operating severity.
Commercial plants: Hydro operated a demonstration unit that

was installed in Norway in 1995. The first commercial MTO

unit is planned for startup in 2008 in Nigeria.
Licensor: UOP LLC/Hydro.

(1). Fluidized-bed reactors (2). Continuous catalyst regenerator

(3). Water removal unit
(4). CO2 removal system (5). Dryer
(6). Deethanizer (7). An acetylene saturation unit
(8). Demethanizer
(9). Depropanizer

MTO PROCESS

Olefins by dehydrogenation
Application:
The Uhde STeam Active Reforming STAR process produces
(a) propylene as feedstock for polypropylene, propylene oxide,
cumene, acrylonitrile or other propylene derivatives, and
(b) butylenes as feedstock for methyl tertiary butyl ether (MTBE),
alkylate, isooctane, polybutylenes or other butylene derivatives.
Feed:
Liquefied petroleum gas (LPG) from gas fields, gas condensate fields and
refineries.
Product:
Propylene (polymer- or chemical-grade); isobutylene; n-butylenes;
high-purity hydrogen (H2) may also be produced as a byproduct.

Description:
The fresh paraffin feedstock is combined with paraffin
recycle and internally generated steam.
After preheating, the feed is sent to the reaction section. This
section consists of an externally fired tubular fixed-bed
reactor (Uhde reformer) connected in series with an
adiabatic fixed-bed oxyreactor (secondary reformer type).
In the reformer, the endothermic dehydrogenation reaction
takes place over a proprietary, noble metal catalyst.
In the adiabatic oxyreactor, part of the hydrogen from the
intermediate product leaving the reformer is selectively
converted with added oxygen or air, thereby forming steam.

 This is followed by further dehydrogenation over the same noble

metal catalyst.
Exothermic selective H2 conversion in the oxyreactor increases
olefin product space-time yield and supplies heat for further
endothermic dehydrogenation.
The reaction takes place at temperatures between 500C 600C
and at 4 bar 6 bar
The Uhde reformer is top-fi red and has a proprietary cold
outlet manifold system to enhance reliability.
Heat recovery utilizes process heat for high-pressure steam
generation, feed preheat and for heat required in the
fractionation section.

 After cooling and condensate separation, the product is

subsequently compressed, light-ends are separated and the olefin

product is separated from unconverted paraffins in the
fractionation section.
Apart from light-ends, which are internally used as fuel gas, the
olefin is the only product. High-purity H2 may optionally be
recovered from light-ends in the gas separation section.
Commercial plants: Two commercial plants using the STAR
process for dehydrogenation of isobutane to isobutylene have
been commissioned (in the US and Argentina). More than 60
Uhde reformers and 25 Uhde secondary reformers have been
constructed worldwide.
Licensor: Uhde GmbH.

Olefins by dehydrogenation