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Ethylene, propylene and butadiene Ethylene, propylene and butadiene

production production
Ethene Ethene and and propene propene
Ethene
- The largest volume building block for many petrochemicals
- Used for the production of many end products such as plastics,
resins, fibers etc.
- Ethylene is produced mainly from petroleum-based feedstock by
thermal steam cracking, although alternative methods are also
gaining importance
Propene
- One of the principal light olefins
- Used widely in plastics as polypropylene and in chemicals e g Used widely in plastics as polypropylene, and in chemicals e.g.
acrylonitrile, propylene oxide, 2-propanol, and cumene
- Produced mainly as a by-product of petroleum refining (FCC
process), of ethylene production by steam cracking and via
dehydrogenation of propane
2
alcohols.
6%
Other
9%
polyethylene
HD
24% Styrene
7%
Ethene Ethene and and propene uses propene uses
Ethylene
oxide
14%
Polyethylene
LD
27%
Vinylchloride
13%
7%
Oth 6%
Oxoalcohols
C
2
H
4
Acrylic Acid 3%
Polypropylene
64%
Propylene
Oxide 7%
Acrylonitrile
10%
Other 6%
Oxoalcohols
7%
Cumene 3%
C
3
H
6
Butadiene Butadiene
Very important intermediate mainly for polymer production
Most of butadiene is used in styrene-butadiene rubber (SBR)
production for the tire industry (28%)
Other polymers: Polybutadiene (PB), styrene-butadiene latex
(SBL), acrylonitrile-butadiene-styrene (ABS)
As intermediate for monomers: adiponitrile, chloroprene, isoprene
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Growth of petrochemical industry Growth of petrochemical industry
Production of the six major
base chemicals:
Ethene
Propene
Butadiene
Toluene
Xylenes
Annual production
Annual growth
Ethene 90 3.6
Propene 60 4.7
Butadiene 10 3.3
p
2004, million t/a
Annual growth
rate, %
Ethylene production Ethylene production
Industrial process
Steam cracking of hydrocarbons (petroleum fractions) ranging from
ethane to heavy gas oil ethane to heavy gas oil
Processes under development
Membrane dehydrogenation of ethane
Oxydehydrogenation of ethane
Oxidative Coupling of methane
Methanol to ethylene
Dehydration of ethanol Dehydration of ethanol
Ethylene from coal
Disproportionation of propylene
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Steam cracker feedstock Steam cracker feedstock
Yield,%
Ethane Propane Naphtha Gas oil
Ethene 76 42 31 23
Propene 3 16 16 14
Butadiene 2 5 9 9
Feed
Propene Propene production production
Steam cracking (65-70%)
Propylene is the primary ethylene co-product from steam crackers
Recovery from refinery streams (25-30%)
Propylene is produced as a dilute stream in propane mainly from - Fluid
catalytic cracking
On purpose processes (2-3%)
Dehydrogenation, metathesis, MTP
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Butadiene production Butadiene production
Over 95% is produced via steam cracking
Feedstock Butadiene fraction
Ethane 1 - 2 Ethane 1 - 2
Propane 4 7
Butane 7 - 11
Naphtha 12 - 15
Gasoil 18 - 24
Butadiene fraction in kg per 100 kg ethene with different feedstocks
EU i th f t t l USA i th f t hth
Catalytic dehydrogenation of n-butane and n-butene (Houdry process)
Oxidative dehydrogenation of n-butene (Oxo-D or O-X-D process)
EU: in the future more natural gas; USA: in the future more naphtha
Steam cracking mechanism Steam cracking mechanism
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Steam cracking mechanism Steam cracking mechanism
Initiation
Two radicals are produced for every paraffin molecule
When naphtanes are involved, diradicals are produced
For aromatics with side chains, H

radicals are produced
Propagation
Many types of reactions are involved including H abstraction, addition, and
radical decomposition
Termination
Radical termination is the reverse of initiation
Ethane as feed
17-21 GJ/t ethene
Naphtha as feed
26-31 GJ/t ethene
Energy requirements
for ethene production
Thermal cracking of higher alkanes
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Thermodynamics of Thermodynamics of lower alkenes lower alkenes dehydrogenation dehydrogenation
Reaction temperature should be
high for sufficient conversion.
F d ti i l f d b Forward reaction is also favored by
a low partial pressure of alkanes,
because for every molecule
converted two molecules are
formed
A process under vacuum would be
desirable in this respect.
It is more convenient to apply
dilution with steam.
The smaller the alkane, the higher
temperature is needed for a given
conversion.
Kinetics of cracking Kinetics of cracking
J 4
Slide 14
J 4 seite 113
J ohannes, 3/10/2008
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Kinetics of cracking Kinetics of cracking
The reactivity increases with chain length
Ethane shows the lowest reactivity
The first-order kinetics implies that the rate of reaction (but not the
conversion) increases with increasing partial pressures of the reactants
However, at higher partial pressures of the reactants, and thus also of the
products, unfavorable secondary reactions, such as condensation
reactions and the formation of coke, occur more frequently
Hence, the partial pressure of HC must be kept low.
For the same reason, conversions should not be too high.
Coke deposition
Secondary condensation reactions lead to coke deposited on the
reactor walls
Problems arising
Reduced heat transfer rates
Increased pressure drop
Lowered yields
Reduced alkenes selectivity
Coke removal Coke removal
Gasification of coke in air and/ or steam
Units are periodically shut down (every 14-100 days)
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Key points of steam cracking process Key points of steam cracking process
High temperature
High heat input
Low hydrocarbon partial pressure y p p
Short residence time
Efficient quench
Low pressure drop
Steam cracking process Steam cracking process
refrigeration
Hydrogen and
methane
refrigeration
Methane
Hydrogen
Diluent
steam
Ethylene
product
Initial
feed furnace
Transfer
line
exchanger
C.W
dryer
refrigeration
Condensate
stripper
DeMethanizer
DeEthanizer
C2 splitter
C3 splitter
Propylene
product
Ethane/propane
recycle
C4+ to fuel
Water to recovery
Quench
tower
Tar to disposal
Heavies to fuel
Separator
pp
DePropanizer
C4+ to fuel
IPRO 304-d
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Typical flow diagram for Typical flow diagram for
naphtha steam cracker naphtha steam cracker
Simplified scheme of a steam cracker
Requirements
Considerable heat input
t hi h t t l l at high temperature level
Limitation of hydrocarbon partial
Pressure
Very short residence time (<1s)
Rapid quench of the reaction
products to preserve the composition products to preserve the composition
Steam is used to minimize side reactions forming coke and to
improve the selectivity by lowering the hydrocarbon partial pressure
Steam/naphtha =50/50 wt
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Steam cracker characteristics Steam cracker characteristics
Steam cracker characteristics
Typical plant up to 500 t/a
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Product processing: gaseous feed Product processing: gaseous feed
Gaseous
Ethane & propane recycle
Water
Hydrogen
Methane
Ethene
Cracking
Water quench
TLE
Compression
Acid gas
Compression
Demethanizer
Gas drying
Deethanizer
Propene
Ethene
factionation
C2H2
Hydrogenation
C3H4
Feedstock
Steam
H2S
Propene
C4
pygas
g
removal
Depropanizer
Propene
fractionation
C3H4
hydrogenation
H2S
CO2
Butadiene recovery Butadiene recovery
Chemical: Exxon CAA-process (cuprous ammonium acetate).
Reversible complexation of butadiene with [Cu(NH
3
)
2
]OAc.
Disadvantages:
O f f f Only for feeds with small amounts of acetylenes
Complex regeneration
Physical: extractive distillation. Butadiene volatility is
decreased by adding of solvents: acetone, furfural, acetonitrile,
dimethylacetamide, dimethylformamide, N-methylpyrrolidone
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Butadiene recovery via reactive distillation process
Hydrogenation step before extractive distillation to convert
acetylenes into corresponding olefins and dienes (Cu/Al
2
O
3
)
Conversion of vinylacetylene into butadiene
Maximizing
butadiene
Hoechst HTP process Hoechst HTP process
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BASF cracking of crude oil BASF cracking of crude oil
The generator A contains a fluidized
(steam and O
2
used fluidization) bed of
coke spheres
Crude oil is injected. Petroleum coke
made is removed made is removed
Cracking takes places at 720 C, coke
particles carried up from the generator
are separated from the vapors and
gases in the cyclone B and returned to
the generator
Column D serves as primary
fractionator, it takes off a heavy bottom
product which serves as fuel. The top
temperature is held at about 100 C so temperature is held at about 100 C so
that the condensation of the water
vapor is just avoided.
Gas (containing some C
5
and heavier),
a highly aromatic light liquid and water
are crudely separated in Separator E
Catalytic cracking of olefinic streams Catalytic cracking of olefinic streams
Main products : propene
ethene
Feed: FCC-naphtha, coker naphtha, pyrolysis gasoline and C4/C5 streams
Reactions: Oligomerisation
Cracking
butenes
Catalyst: ZSM-5
g
Disproportionation
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Catalytic cracking process for propylene Catalytic cracking process for propylene
Licensors :Mobil (MOISM),
Kellogg Brown & Root (SUPERFLEXSM)
Lurgi (PROPYLUR), EXXON (PCC)
The C3 stream contains 85-90% propylene
Catalytic dehydrogenation of propane to propylene
C
n
H
2n+2
C
n
H
2n
+ H
2
= 125 - 138 kJ/mol
Drawbacks
Thermodynamic restrictions on
conversion and selectivity
Side reactions (thermal cracking)
Strong endothermicity
Rapid formation of coke
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Catalytic dehydrogenation for Catalytic dehydrogenation for propene propene production production
Process Reactor Catalyst
T (C)
P (bar)
Conversion
(%)
Selectivity
(%)
Oleflex
(UOP)
Adiabatic
moving
bed
Pt/Al
2
O
3
550-620
2
25 89-91
Catofin
(ABB
Lummus)
Adiabatic
fixed bed
Cr/Al
2
O
3
570-630
0.5
48-65 82-87
STAR Tubular Pt-Sn/Zn- 480-620 S
(Krupp-Uhde)
Tubular
reactors
t S /
Al
2
O
3
80 6 0
5
30-40 80-90
FBD-4
(Snamprog-
Yarsintez)
Fluidized
bed
Cr/Al
2
O
3
550-600
1.3
40 89
Commercial reactors for propane dehydrogenation Commercial reactors for propane dehydrogenation
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Membrane dehydrogenation for Membrane dehydrogenation for ethene ethene production production
Conventional, multiple, fixed-bed catalytic reactors are used for
dehydrogenation y g
After each bed, the hydrogen is partially separated using membranes to shift
the equilibrium
Ceramic and other inorganic membranes that can be used at high temperatures
(600C and above)
Catalyst-coated membranes can be used for reaction and separation
The achievable conversion depends on the permeability of the membrane
Since separation is independent of reaction, reaction temperature can be
ti i d f i f optimized for superior performance
Oxydehydrogenation Oxydehydrogenation
Because of the limitations of light alkanes dehydrogenation equilibrium,
research has focused on ways to remove one of the products, namely
hydrogen, by chemical methods hydrogen, by chemical methods
In this way, hydrogen is oxidized to water and there is no equilibrium limitation
C
n
H
2n+2
C
n
H
2n
+ H
2
endothermic
H
2
+ O
2
H
2
O highly exothermic
C
n
H
2n+2
+ O
2
C
n
H
2n
+ H
2
O exothermic
However, the same oxygen also oxidizes ethane and ethylene to CO
2
and other
oxygenated products. Therefore, selectivity to olefins is a serious
consideration
Not commercially available
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Catalytic Catalytic pyrolysis pyrolysis
Catalytic pyrolysis is aimed at producing primarily ethylene
Almost all catalysts produce higher amounts of CO and CO
2
than
ll bt i d ith ti l l i normally obtained with conventional pyrolysis
This indicates that the water gas shift reaction is also very active
in these catalysts (low surface area alumina catalysts), and usually lead
to some deterioration of the olefin yield
Notable exception, the catalyst contains vanadium as the active material
on pumice is claimed to produce low levels of carbon dioxides
Vast reserves of remote gas
L i th l f
Gas refineries of the future
Indirect natural gas conversion to olefins - MTO
MTO
Low price methanol from mega-
methanol plants
Ethylene
Propylene
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Methanol to Methanol to ethene/propene ethene/propene - - MTO MTO
Zeolite based catalysts
- Ni/SAPO34 with almost 95% selectivity to ethylene
- ZSM5 propene dominating product
Methanol is converted to dimethyl ether, which decomposes to ethylene and
water
2 CH
3
OH H
3
C-O-CH
3
+ H
2
O H
298
= -23.6 kJ/mol
H
3
C-O-CH
3
H
2
C=CH
2
+ H
2
O H
298
= -5.5 kJ/mol
H
2
C=CH
2
+ CH
3
OH CH
2
=CH-CH
3
+ H
2
O
By optimizing the catalyst and process conditions yields of ethene and
propene can be maximized propene can be maximized
Processes licensors
- Lurgi (mostly propene)
- UOP/HYDRO (ethene and propene)
UOP / HYDRO MTO process UOP / HYDRO MTO process
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MTP MTP--Lurgi Lurgi process process
Fixed bed reactor
Selective zeolite based catalyst
Ethanol to Ethanol to ethene ethene
The economics of this process depends on the availability and prices of ethanol
Offers advantages to a country with abundant fermentation ethanol but limited
hydrocarbon resources hydrocarbon resources
Catalysts: Activated alumina and phosphoric acid on suitable support or zinc
oxide with alumina
Commercially available process include the Lummus processes (fixed and
fluidized-bed processes), Halcon/Scientific Design process, NIKK/JGC
process, and the Petrobras process
Typical ethene yield is between 94 and 99% in all these processes
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Propylene Propylene disproportionation disproportionation
Since the above reaction is reversible, it can be used to produce either
2 C
3
H
6
C
2
H
4
+ C
4
H
8
, p
propylene or ethylene and butenes depending on relative prices.
A commercial plant utilizing the disproportionation of propylene to ethylene was
built in 1966 by Gulf Oil of Canada Ltd utilizing technology developed by
Phillips.
A commercial plant based on the reverse reaction has been built on the Gulf
Coast .
ABB olefins conversion technology ABB olefins conversion technology
The olefins conversion (OCT) from ABB is used to combine n-butenes with
ethylene to produce polymer-grade propylene
Two chemical reactions take place :
- Propylene is formed by metathesis of ethylene and butene-2
- Butene-1 is isomerized to butene-2, as butene-2 is consumed in the
metathesis reaction
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ABB olefins conversion technology ABB olefins conversion technology
Improves C
4
processing economics by converting pyrolysis C
4
s to propylene
Since the reaction system does not regenerate any propane, the propane /
propylene separation is not required
Fixed bed catalyst system with in situ regeneration for simple operation Fixed bed catalyst system with in situ regeneration for simple operation.
The OCT can be integrated with a steam cracker
The OCT can be integrated with a fluid catalytic cracker
Butene conversions 60 - 75% with greater than 95% selectivity to propylene
Downer catalytic Downer catalytic pyrolysis pyrolysis (DCP) process (DCP) process
Gas and solid flow downwards
leading to a more uniform radial flow
structure
The axial backmixing of gas and solid
is minimal
High velocity of particles caused by
the down flow movement will result in
a shorter contact time in comparison
with the upflow systems
The gas need not suspend the
particles so that low pressures can be
T : 659 C
P: 0.005 Mpa
t : 0.75 s
Zeolite catalyst
particles so that low pressures can be
used; permits the adoption of a large
catalyst to oil ratio (C/O)
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Other processes for olefin production Other processes for olefin production
Process Temperature
(C)
Catalyst Feed Desired
Products
Tubular furnace 840 no Daqian Naphtha Light olefins
Lurgis sand
furnace
730 sand Distillates of
crude oil
Light olefins
K-K process 749 Coke particle Arabic light oil Light olefins
Asahi Process 680 Fe/zeolite Light
hydrocarbons
Ethylene +
Propylene
Vniios process 770-820 Potassium
vanadate/
supporter
Many feeds Ethylene +
Propylene
TCSC process 810 Calcium aluminate VGO Ethylene +
Propylene
CPP 720 CPC Wax oil Ethylene +
Propylene
PetroFCC 538 - 566 USY + ZSM-5 Heavy feeds Propylene
Lower alkenes from oil Lower alkenes from oil
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Lower alkenes from gas Lower alkenes from gas
Lurgi Lurgi - - Ruhrgas Ruhrgas sand cracker sand cracker
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Lurgi Lurgi - - Ruhrgas Ruhrgas sand cracker sand cracker
a) The feed is preheated in the second washer/cooler (14), vaporized in feed vaporizer
(12), superheated in feed super heater (3), and reacted in the hot sand (8)
b) In the first washer/cooler (10) the cracked gas is cooled whilst sand dust, free carbon
and highly condensed polymers are washed out. The circulating wash oil rises in
temperature from 250 to 300 C and is brought back to 250 C in feed vaporizer (12)
and steam raising (13).
c) In the second washer/cooler (14) circulation of a middle range wash-oil helps transfer
heat from the cracked gas to the tube bundles, which serve to heat the fresh feed and
water used in steam raising.
d) Reaction stop by quenching after 0.3 0.5 seconds
e) Reaction temperature: 700 850 C
f) The quench to 50 - 100C below reaction temperature is required. This is effected by f) The quench to 50 100 C below reaction temperature is required. This is effected by
spraying light distillate into the top (exit end for vapour) of the reactor. The light
distillates are in part cracked and give some additional olefins.
g) The sand in the reactor moves down through guide plates and forms essentially a
series of boiling beds.
Kellog Kellog--ICI steam cracking ICI steam cracking
C
Steam is added in the ratio 0.3
tons to 1 ton of light distillate at
entry to the oil heater F, and only
25 percent conversion to gas take
place in E At this low degree of
A
B
F
D
E
place in E. At this low degree of
cracking there is no coke lay down.
Cracking is completed in the
soaker line A by adding a further
two tons of steam superheated to
925C in the steam heater F
The soaking time is 1 2 sec,
when the vapors are quenched in
B which recovers equal to 60
A Soaker Line, B Quench Boiler
C Boiler Drum, D Fractionator
E Oil Heater, F Steam Heater
B, which recovers equal to 60
percent of that used
Fractionator D not only separates
the heavy oil but cools and scrubs
the vapors from tar mist. Gaseous
hydrocarbon products are
removed.