Energy Efficiency and Innovative Emerging

Technologies for Olefin Production

T. Ren
Utrecht University, The Netherlands
Email: t.ren@chem.uu.nl, Heidelberglaan 2, 3584 CS
Sponsored by Utrecht Energy Research Center (UCE) and
Energy Research Foundation (ECN)

European Conference on Energy Efficiency

in IPPC-Installations
On October 21-22, 2004 in Vienna, Austria

Copernicus Institute
Sustainable Development and Transition Management
 In this presentation

Introduction to olefins
Energy use and CO2 emissions
Energy analysis
State-of-the-art
Innovations
Conclusion
Next step
Where is the Olefin Industry?

IPTS 2000
Light olefins and Steam Cracking

Ethylene (C2H4) and

Propylene (C3H6)
are two most important light olefins

They are the building blocks

of the chemical industry.
Their production process, steam cracking,
has the backbone status for the sector.
Used in the production of plastics, fibers, lubricants, films,
textiles, pharmaceuticals, etc. ---even chewing gum!
BASF 2000

Steam
Cracking
 Energy Use and Emission
from Steam Cracking
Steam cracking is the single most energy
consuming processes in the chemical industry

ca. 30% of the sectors total final energy use

and ca. 180 millions tons of CO2 in 2004

Another reason for innovation:

over 35% of European crackers are over 25 years old
 Estimated Global Energy Use and Emission 2004

Europe (including new EU

World US
member states and FSU)

Total feedstock (Million

300 85 90
tons)

naphtha 55, ethane 55, naphtha 75,

Breakdown of ethane 30, naphtha 23, LPG 10,
Feedstock (wt. %) LPG 10, propane15, gas oil 9,
gas oil 5 gas oil 5 ethane 5

Ethylene capacity 30-32 (23-24 by

110-113 28-30
(Million tons) Western Europe)

Propylene capacity
53-55 16-17 17-18
(Million tons)

Total process energy

(fuel combustion and
2-3 0.5-0.6 0.7-0.8
utilities
included) (EJ)
Total CO2 emission
(fuel combustion, decoking
180-200 43-45 53-55
and utilities included)
(Million tons)
Conventional Naphtha-based Steam Cracking Process

IPPC/BREF 2001
A naphtha steam cracker (900 kt/a) at Shell Moerdijk, the Netherlands

Shell 2003
 Energy/Exergy Analysis
Ethane Naphtha

Process
Process Energy Exergy loss
Energy
[27] [31] Our [80]
[26]
estimate [20]
Fuel combustion
Heat of 73%
23% and heat transfer to 75% (or
Pyrol reaction
65% the furnace 15 GJ/t N/A
ysis Steam, Heat exchange with
24% ethylene) 27%
heating steam, TLEs and
&losses heat loss to flue gas
Fractionation and 22% 15% Fractionationf and 19%
Compression Compression
12%
De-methanization
25% (2
De-ethanizer and GJ/t 23%
C2 splitter ethylene
in 2%
C3 splitter N/A
compressio
Separation 31% 20% n and the
De-propanization/ rest of 10%
De-butanization separation
processes)
Ethylene 5%
refrigeration
Propylene 30%
refrigeration
100% or 100% (only 100% (only
Total process
100% 100% Total exergy losses 17 GJ/t pyrolysis compression
energy use
ethylene section) and separation)
 Conclusions from Energy Analysis

Pyrolysis section is the most energy

consuming section (65% of the total energy
use and 75% the total exergy losses)
Also energy consuming (each ca. 15-20%):
Refrigeration and C2 separation
Fractionation and compression
 State-of-the-Art Naphtha Steam Cracking Processes

Licensors Technip-Coflexip ABB Lummus Linde AG Stone & Webster Kellogg & Brown Root

Twin-radiant-cell
Radiant coils Double pass radiant Coil design (straight,
Coil related design (single split) Twin-radiant-cell
pretreated to reduce coil design; online small diameter), low
furnace is 13m (shorter than design and quadra-
coking with a sulfur- decoking reduces reaction time; very high
features the average length cracking
silica mixture emissions severity
25m)
De-
De-methanization
methanizer Double De-methanizer with Front-end de- Absorption-based
simultaneous mass
separation de-methanizing low refrigeration methanizer and demethanization system
transfer and heat
features stripping system demand hydrogenation with front-end design
transfer

Gas Turbine Ca. 3 GJ/t

N/a N/a Offered but no data N/a
ethylene saved

Ethylene
Yield 35% 34.4% 35% N/a 38%
(wt. %)
SEC
18.8-20 (best)
(GJ/t 18 (with gas turbine);
or 21.6-25.2 (typical) 21 (best) 20-25 No data
ethylene) 21 (typical)

Conclusion: 20% of energy savings on the current energy use

(25-30 GJ/t ethylene) of naphtha steam cracking are possible.
 Advanced naphtha steam cracking

Advanced furnace materials (e.g. low coking

coating)
Vacuum Swing Adsorption, mechanical vapor
recompression
Advanced distillation columns, membrane and
combined refrigeration systems

Conclusion: up to 20% energy savings are possible in

the pyrolysis section and up to 15% energy savings are
possible in the compression and separation sections.
 Innovative Olefin Technologies

Ethane Propane Catalytic Hydro-

Gas Stream Byproduct upgrading Catalytic Pyrolysis
Oxidative De- Oxidative cracking of pyrolysis of
Technologies (C4-9) Process (CPP)
hydrogenation dehydrogenation naphtha Naphtha

Ethane and Crude oil, refinery

Ethane and Propane and
Feed other gas Naphtha Naphtha C4-C9 (from steam heavy oils, residues,
oxygen oxygen
feedstock cracking, refinery, etc.) atmospheric gas oil,
vacuum gas oil

Olefins Ethylene Ethylene Propylene Ethylene/propylene Ethylene Propylene Ethylene/propylene

Shockwave,
Both a stem Reactors with
combustion Alloy Catalyst
Reactor reformer and an Fluidized bed hydrogen co Riser and transfer line
gas; shift Reactor with Fixed or fluidized bed
(oxy-reactor); or, feed but less reactor
syngas; hydrogen co feed
cyclic fixed-bed steam
plasma; etc.

Zinc and calcium Zeolite (or various Acidic zeolite (Lewis

N/a Zeolite
N/a Mordenite zeolite aluminate based metal oxides) sites)
Catalyst

Temp. 625-700 900-1100 550-600 650-680 785-825 580-650 650-750

oC

Blachownia: ca.
Process Uhde: ca. 8-10
Shockwave: Dow: ca. 10-12 KRICT: ca. 19 GJ/t 16-20 GJ/t CPP: ca. 35 GJ/t
energy GJ/t propylene; N/a
ca. 8-10 GJ/t GJ/t ethylene and ca. 10 ethylene and ethylene and ca. 12
(SEC)i ca. 8-10 GJ/t
ethylene/HVCs ethylene/HVCs GJ/t HVCs ca. 10-13 GJ/t GJ/t HVCs
HVCs
HVCs
Dow: final
Uhde: propylene KRICT: ethylene Blachownia: CPP: ethylene 21%,
Shockwave: ethylene ca. 53% UOP: total propylene
Yield final yield ca. 38%, propylene Ethylene yield propylene 18%, C4
highest if yield from steam
(wt. %)j 78% if weighted 17-20%, aromatics 36-40% and 11%, aromatics 15%
ethylene yield weighted against cracking is 30% and
against propane 30% and HVCs HVCs yield and
ca. 90% ethane and HVCs yield 85%
and oxygen 73% 70% HVCs yield 60%
oxygen
Current
Commercially Commercially Lab and near
status Lab Lab Pilot plant Commercially available
available available commercialization
 CHEEC Project
by Dow and SABIC (NL)

CHEEC (Cheap Energy Efficient Ethylene

Cracking)catalytic olefin technology!
Yield of ethylene and propylene together up
by 24%
Energy use reduced by 20%
Investment lowered by 27% and variable
costs lowered by 14%
Novem 2003
Conclusions from Innovative Olefin Technologies

Catalytic olefin technologies produce high yield

of valuable chemicals (in particular) propylene
from low-cost feedstocks at lower reaction
temperature
Special reactors, catalysts or additional materials
(oxygen, hydrogen, etc.) can be applied to reduce
energy consumption
Up to ca. 20% energy savings are possible (on 11-
14 GJ/t high value chemicals of energy use by
state-of-the-art naphtha steam cracking)
 Overall Conclusions
Pyrolysis section is the most energy
consuming in a steam cracker
Plenty of room for energy savings is
possible in steam cracking
Catalytic olefin technologies can lead to
energy saving (up to 20%) on energy use
by state-of-the-art steam cracking
Ca. 90% chemical processes already benefits from catalysis,
so can steam cracking!
 Our Next Step
Energy and economic
analysis for Natural gas-
to-Olefin technologies
have been completed
one conclusion is that at
this moment there are no
energy saving (75% more
energy use and only
feasible in locations where
prices of natural gas are
very low $0.75-1.0/GJ)
Barriers/drivers and
their implications for
innovation in the
(bulk) chemical
industry are being
studied
Policies and strategies
for stimulating
innovation will be
recommended
Thank you! Questions?
 Some Backup Sheets
Why Do Catalytic Olefin Technologies Save Energy?

Energy saving!
Energy

Ren 2003

Process energy required in a pyrolysis furnace

Activation Energy In the case of conventional steam cracking
without catalysts
Process energy required in a reactor
In the case of catalytic olefin technologies
Activation Energy
with catalysts

Thermodynamic Olefins and byproducts

energy requirement

Ethane, naphtha or other feedstocks

Progress of Cracking Process

 Simplified Chemical Reactions by Conventional
Naphtha Cracking (or Thermal Cracking)

Naphtha

Thermal Cracking

Free radicals

Reorganization

Ethylene Propylene
 Simplified Chemical Reactions by
Catalytic Naphtha Cracking

Naphtha

Thermal cracking Catalytic cracking

etc. etc.

Free radicals Carbonium ions

Zeolite Catalysts

Reorganization

Propylene
Ethylene
 Drivers/Barriers (1/2)
Economic Drivers Economic Barriers

Lower energy costs New plant investment in

Value added (from the range of 500 million
low-cost feedstock to to 1 billion euros
high value chemicals) Most old plants run with
Strong propylene zero depreciation, low
demand margins and over-
capacity
 Drivers/Barriers (2/2)
Technical Drivers Technical Barriers

Rapid advances in Low olefin yield and

R&D on new catalysts high byproduct yield
Spillover from Reaction and oxygen
extensive technical use
experience in refinery Coking and spent
catalysts catalysts