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!

Steam Cracking BASF 2000

Energy Use and Emission from Steam Cracking Steam cracking is the single most energy consuming processes in the chemical industry ca. 30% of the sector’s 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   World US Europe (including new EU member states and FSU) Total feedstock (Million tons) 300 85 90 Breakdown of Feedstock (wt. %) naphtha 55, ethane 30, LPG 10, gas oil 5 ethane 55, naphtha 23, propane15, naphtha 75, gas oil 9, ethane 5 Ethylene capacity (Million tons) 110-113 28-30 30-32 (23-24 by Western Europe) Propylene capacity 53-55 16-17 17-18 Total process energy (fuel combustion and utilities included) (EJ) 2-3 0.5-0.6 0.7-0.8 Total CO2 emission (fuel combustion, decoking and utilities included) (Million tons) 180-200 43-45 e CO2 emission and process energy use are based on [32] and [5]. Decoking data is from [29]. US figures are lower than those of Europe due the fact that heavy feedstocks use more energy use in total.

Conventional Naphtha-based Steam Cracking Process IPPC/BREF 2001

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

Energy/Exergy Analysis   Ethane Naphtha Process Energy Exergy loss [27] [31] Our estimate [26] [80] [20] Pyrolysis Heat of reaction 23% 65% Fuel combustion and heat transfer to the furnace 75% (or 15 GJ/t ethylene) 73% N/A Steam, heating &losses 24% Heat exchange with steam, TLEs and heat loss to flue gas 27% Fractionation and Compression 22% 15% Fractionationf and Compression 25% (2 GJ/t ethylene in compression and the rest of separation processes) 19% Separation 31% 20% De-methanization 12% De-ethanizer and C2 splitter C3 splitter 2% De-propanization/ De-butanization 10% Ethylene refrigeration 5% Propylene refrigeration 30% Total process energy use 100% Total exergy losses 100% or 17 GJ/t ethylene 100% (only pyrolysis section) 100% (only compression 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 Coil related furnace features Radiant coils pretreated to reduce coking with a sulfur-silica mixture Double pass radiant coil design; online decoking reduces emissions Twin-radiant-cell design (single split) is 13m (shorter than the average length 25m) Twin-radiant-cell design and quadra-cracking Coil design (straight, small diameter), low reaction time; very high severity De-methanizer separation Double de-methanizing stripping system De-methanizer with low refrigeration demand Front-end de-methanizer and hydrogenation De-methanization simultaneous mass transfer and heat transfer Absorption-based demethanization system with front-end design Gas Turbine N/a Ca. 3 GJ/t ethylene saved Offered but no data Ethylene Yield (wt. %) 35% 34.4% 38% SEC (GJ/t ethylene) 18.8-20 (best) or 21.6-25.2 (typical) 18 (with gas turbine); 21 (typical) 21 (best) 20-25 No data 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 Gas Stream Technologies Ethane Oxidative De-hydrogenation Propane Oxidative dehydrogenation Catalytic cracking of naphtha Hydro-pyrolysis of Naphtha Byproduct upgrading (C4-9) Catalytic Pyrolysis Process (CPP) Feed Ethane and other gas feedstock Ethane and oxygen Propane and oxygen Naphtha C4-C9 (from steam cracking, refinery, etc.) Crude oil, refinery heavy oils, residues, atmospheric gas oil, vacuum gas oil Olefins Ethylene Propylene Ethylene/propylene Reactor Shockwave, combustion gas; shift syngas; plasma; etc. Alloy Catalyst Reactor with hydrogen co feed Both a stem reformer and an (oxy-reactor); or, cyclic fixed-bed Fluidized bed Reactors with hydrogen co feed but less steam Fixed or fluidized bed Riser and transfer line reactor Catalyst N/a Mordenite zeolite Zinc and calcium aluminate based Zeolite (or various metal oxides) Zeolite Acidic zeolite (Lewis sites) Temp. oC 625-700 900-1100 550-600 650-680 785-825 580-650 650-750 Process energy (SEC)i Shockwave: ca. 8-10 GJ/t ethylene/HVCs Dow: ca. 10-12 GJ/t ethylene/HVCs Uhde: ca. 8-10 GJ/t propylene; ca. 8-10 GJ/t HVCs KRICT: ca. 19 GJ/t ethylene and ca. 10 GJ/t HVCs Blachownia: ca. 16-20 GJ/t ethylene and ca. 10-13 GJ/t HVCs CPP: ca. 35 GJ/t ethylene and ca. 12 GJ/t HVCs Yield (wt. %)j Shockwave: highest ethylene yield ca. 90% Dow: final ethylene ca. 53% if weighted against ethane and oxygen Uhde: propylene final yield ca. 78% if weighted against propane and oxygen KRICT: ethylene 38%, propylene 17-20%, aromatics 30% and HVCs 73% Blachownia: Ethylene yield 36-40% and HVCs yield 70% UOP: total propylene yield from steam cracking is 30% and HVCs yield 85% CPP: ethylene 21%, propylene 18%, C4 11%, aromatics 15% and HVCs yield 60% Current status Lab Commercially available Pilot plant Lab and near 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)

Ca. 90% chemical processes already benefits from catalysis, 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? Progress of Cracking Process Energy Ethane, naphtha or other feedstocks Olefins and byproducts Activation Energy without catalysts with catalysts Thermodynamic energy requirement Process energy required in a pyrolysis furnace In the case of conventional steam cracking Process energy required in a reactor In the case of catalytic olefin technologies Energy saving! Ren 2003

Naphtha Thermal Cracking Free radicals Reorganization Ethylene Simplified Chemical Reactions by Conventional Naphtha Cracking (or Thermal Cracking) Thermal Cracking Naphtha Free radicals Reorganization Ethylene Propylene

Simplified Chemical Reactions by Catalytic Naphtha Cracking Thermal cracking Naphtha Catalytic cracking Free radicals Zeolite Catalysts Carbonium ions etc. Reorganization Ethylene Propylene

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

Drivers/Barriers (2/2) Technical Drivers Rapid advances in R&D on new catalysts Spillover from extensive technical experience in refinery catalysts Technical Barriers Low olefin yield and high byproduct yield Reaction and oxygen use Coking and “spent catalysts”