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42. Tutzing-Symposion, March 2 nd , 2004

TRENDS IN FOSSILE BASED RAW MATERIALS. Giuseppe Bellussi, Paolo Pollesel. 42. Tutzing-Symposion, March 2 nd , 2004. 1. SUMMARY. Fossil resources: trends, availability Technologies for resources exploitation and upgrading Raw materials for petrochemical

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42. Tutzing-Symposion, March 2 nd , 2004

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  1. TRENDS IN FOSSILE BASED RAW MATERIALS Giuseppe Bellussi, Paolo Pollesel 42. Tutzing-Symposion, March 2nd, 2004 1

  2. SUMMARY • Fossil resources: trends, availability • Technologies for resources exploitation and upgrading • Raw materials for petrochemical • Refinery/petrochemical integration • Raw materials from biological sources • Conclusions1 2

  3. From raw materials to chemicals Crops (biomass) Natural gas Oil Coal Building blocks Commodities Fine chemicals 3

  4. World energy demand Raw materials scenario is mainly driven by energy demand European Commission – World Energy, Technology and Climate Policy Outlook - WETO 2030 4

  5. Upstream: drivers and scenario for oil 1 0 8 . 5 m b d 2020 C o n d e n s a t e s E x t r a - h e a v y o i l ( < 1 0 ° A P I ) : m i n e a b l e o i l s a n d s , b i t u m e n ( i n s i t u ) , a n d O r i n o c o N G L s * U l t r a - d e e p w a t e r o i l ( > 2 , 5 0 0 f e e t ) C r u d e 7 0 . 0 m b d 7 8 . 6 m b d 8 7 . 2 m b d 9 9 . 1 m b d 9 0 9 1 2 0 0 0 2 0 0 5 2 0 1 0 OIL PRODUCTION TREND AND CONTRIBUTIONS (million bar/g) Oil: Demand for final Uses (%) CERA Roundtables, May 2003 5

  6. 50 45 WTI Brent 40 Arabian L. 35 Kuwait API Gravity Arabian H. 30 Daquing Urals Iranian H. 25 20 Maya 15 = 500 mila bbl /d = 500 mila bbl /d 10 0 0.5 1 1.5 2 2.5 3 3.5 4 Sulphur content (%w.) Production volumes and quality for main crudes For the last 10 years average values: 33.5°API, 1.16% w. S. For the future it is expected a decrease of 0.11°API and an increase of 0.016% w. S per year. 6

  7. Gtoe Oil 112% Natural gas 80% 50% Gas/oil ratio of proven reserves 1000 m3 of natural gas= 0.9 toe Natural gas reserves( 1012m3) 50% Natural gas proven reserves have surpassed oil ones Source Cedigaz 2002 7

  8. % of world total 55.9 7.8 31.5% 6.9 4.4% 3.9% 70.7 39.8% 13.1 7.4% 15.2 8.0 8.5% 4.5% World Total: 177.6 1012 m3 Natural gas reserves distribution( 1012 m3) Source Cedigaz 2002 8

  9. “Stranded gas”: most attractive basins Zagros. (Irak) 611,6 Gm3 Arctic Coastal Plain (Alaska) 1136,1 Gm3 Zagros. (Iran) 2364,5 Gm3 Precaspian Basin (Kazakhstan) 373,8 Gm3 East Venezuela (Venezuela) 671,1 Gm3 Talara Basin (Peru) 51,0 Gm3 Nigeria 1670,7 Gm3 Central Arabian Prov. (Kuwait) 56,6 Gm3 Central Arabian Basin (S. Arabia) 409,5 Gm3 From: Remote Gas Development Strategies (Multi Client Study, 1999), Petroconsultants MAI - ZEUS Dev.Corp. 9

  10. Conventional Non conventional 520 tar sands 300 Canada 1028 Conventional OIL 260 Arabia 1165 oil shales 78 Heavy oil Venezuela 500 USA OIL 270 extra HO Venezuela 994 Conventional GAS 1000 about Coalbed methane GAS 156 Stranded gas 6100(conservative) Gas Idrates [billion boep] Strategic importance of non-conventional sources With about 1000 billion barrels of conventional oil and 1000 billion equivalent barrels of natural gas (corresponding to 163.000 Gm3), total estimated non-conventional technically recoverable oil reserves are 2000 billion equivalent barrels. More uncertain are non conventional gas reserves, with the most conservative estimation corresponding to 7 times proven reserves. Eni World Oil & Gas Review, 2002; The Petroleum Economist, 1998; ww.CERA.com; Offshore Technology Conference, 2001 10

  11. Conventional Sources Technological complexity, higher production costs Non conventional Sources The “Resources Triangle” From top to bottom of the triangle the aboundance of the resources increases, but technological difficulties and production costs also grow. Med- high quality oil/gas Low perm. oil Tight gas sands Tar sands Heavy oil Coal-bed methane Gas hydrates Gas shales Oil shale In the next decades, with the decrease in conventional sources reserves and production, there will be a developed market for non-conventional oil and gas. 11

  12. The role of technology Increase of resources availability Technologies for the production of energy/resources Demand of energy/resources Primary Resources Technologies for the use of energy/resources Reduction of energy intensity Technologies have two fundamental roles: • to ensure the exploitation of available primary resources • to efficiently meet the final demand, reducing specific energy/resources consumption 12

  13. Conversion-upgrading technologies Gas to Chemicals processing routes Fuel Gas Fischer-Tropsch synthesis LPG upgrading Naphtha Diesel Waxes Natural Gas Fuel Cells SYNGAS Associated Gas MTC Chemicals (MTBE, ac.acid,HCHO) MtSynfuels Diesel Methanol synthesis MTP Propylene, PP Acrylic acid MTO Ethylene, Prop. MtPower Power, Fuel(DME) MTH Hydrogen From: U. Wagner et al., Gas to Chemicals: Advanced technologies for natural gas monetization, 12th Int. Oil, Gas and petrochemical Conf. 13

  14. Steps of the Fischer-Tropsch process Fischer-Tropsch products hydrocracking products GtL Conversion via Fischer-Tropsch Eni/IFP Pilot Unit Capacity: 20 bpsd (850 t/y) of paraffins Site: Sannazzaro refinery (Italy) Industrial plants First unit by Shell at Bintulu (Malaysia) 12500 bbl/d started up in 1993 Shell has announced a 140000 bbl/d plant in Qatar Conoco-Phillips has announced a 160000bbl/d plant also in Qatar 14

  15. Natural Gas MTO Methanol Synthesis SynGas Production Lights Flue gas Ethylene Propylene Ethylene by-products Propylene Butenes Methanol Heavy End Air Water Innovative technologies for light olefins Methanol to Olefins(via DME) with zeolitic catalysts UOP - NORSK-HYDRO Fluid-bed MTO Technology 15

  16. MTO processes • Mobil Process • more gasoline produced • fluid bed technology / proven at demonstrative level • MTO(UOP/Norsk Hydro) • mixture of ehylene and propylene • fluid bed technology / 2 industrial plants announced* • MTP(Lurgi) • very selective to propylene (71%) • fixed bed technology / proven at pilot level * Lekki: (Nigeria) expected on stream in 2006, capacity 400 kton/y of HDPE Damietta: (Egypt) planned for a capacity of 300 kton/y PE and 250 kton/y PP 16

  17. Eni Slurry Technology (EST) Gas COKING Naphtha Gasoil Coke HT VR Gas Naphtha EST Gasoil CatFeed Purge EST is a new hydroconversion process that can be applied to convert petroleum residues and heavy oils into higher value light oil products and an upgraded deasphalted oil (DAO) to be used as CatFeed, with a minimum byproduct (purge 2-4 wt%). Arabian Light API° 32.7 S 1.8 %w CCR 4.6 %w Ni+V 39 ppm VR(530+) 23 %w Cerro Negro API° 9.3 S 3.9 %w CCR 15.8 %w Ni+V 503 ppm VR(530+) 60 %w Naphtha heavy oil 17

  18. EST process scheme Distillate DAO Feedstock & catalyst make-up Asphaltenes Reactor Fractionation SDA • deep conversion of the feed (98%) • proper catalyst recycling Enitecnologie pilot plant A 1200 bbl/d demo-plant is under construction at the Taranto refinery 18

  19. Heavy Oil SAGD production (Steam Assisted Gravity Drainage) Husky Energy Pike’s Peak Long-stroke pump jack Rotaflex pump Steam lines Injection well 19

  20. CHOPS: Cold Heavy Oil Production with Sand Produced sand from separation stocktanks 20

  21. Steam Cracking FCC, Cat. Reforming Steam Reforming Gasification, P.O. ethylene propylene butadiene, buthens benzene toluene xylenes Petrochemical building blocks COAL OIL NATURAL GAS (saturated hydrocarbons) methane F.T. SYNGAS MTO MTP 21

  22. Main petrochemical raw materials Ethylene and propylene are the most important organic chemicals in the world for production volume 22

  23. Ethylene production feedstock distribution Gas Feed Liquid Feed 40% 1997 60% 37% 2005 63% Ethylene STEAM CRACKING Key Drivers High cost for NG in the USA New installed capacity only in producing countries (especially M.East, Asia) In existing plant need for lower cost feedstock (heavier feeds) 23

  24. To improve selectivity to light olefins • Millisecond Technology (Kellogg) • Metallurgy (internal tube coating, materials, ceramic furnaces) • Use of coke inhibitors (additives, coating with catalytic layers: Veba Pyrocat, SK Corp. Py-coat) To process heavier feedstock • Fluid bed pyrolysis with solid heat carrier(Chevron Thermal Regenerative Cracking – Quick Contact, Lurgi Sand Cracker) • Catalytic pyrolysis with metal oxides catalysts: VNIIOS, Toyo Eng., Linde/Veba with zeolite-type catalysts: RIIP/Sinopec, Asahi, AIST-Toyo • Partial Oxydation (Univ. of Minnesota) Technological needs in S.C. process 24

  25. Changes in refinery scenario Key drivers Changes in gasoline/diesel demand New regulations on fuel quality Increasing in propylene demand Declining demand for fuel-oil 25

  26. W. Europe Motor Gasoline vs Diesel demand (including projections 1993-2010) Source: Cambridge Energy Research Association 20505-1 0418 26

  27. GASOLINE 1999 2000 2005 beyond 2010 Sulphur ppm, max 500 150 50 * 10 Aromatics %v, max - 42 35 * 35 Olefins %v, max - 18 18 18 Benzene %v, max 5 1 1 è 0 TVR Est. kPa, max 70/90# 60/70# 60/70# 60/70# #: artic climate DIESEL 1999 2000 2005 beyond 2010 Sulphur ppm, max 500 350 50 * 10 Density, kg/m3, max 860 845 845 845 Cetane N. min 49 51 51 51 T95 °C, max 370 360 360 360 PAH %p, max - 11 11 11 *: values already set Fuel specificationsTrend of European regulations impact on petrochemical Font: ET elaborations from www.dieselnet.com ed EU regulations 27

  28. Propylene market and technology trends Propylene demand growth is still increasing faster than that for ethylene (ca. 5% vs. 4% yearly) C3=/C2= unbalance with respect to S.C. production ratio Propylene is a by-product of SC or FCC • There is a technological need for reliable and profitable technologies aimed to increase propylene/ethylene ratio downstream S.C. or to produce propylene in local situation. • Decreased demand for gasoline, results in increased availability of naphtha cuts from refinery, which can be used to produce propylene. 28

  29. Propylene via FCC or SChow to increase the production? • FCC catalyst modification • propylene : 7-9%: Maxofin (Mobil-Kellogg), Octamax (Chevron), MIO (Sinopec) • FCC Process modification(fluidized bed design, process conditions, improved separation, …) • propylene up to 25% • Several available technologies : DCC (Sinopec), PetroFCC (UOP), NexCC (Fortum), SCC (ABB), USC (IFP/Total), ... • Downstream processes for cracking of heavier olefinic cuts (Light Cracked Naphtha, C4-C5 da Cracker) to C3= • Several proposed technologies based on ZSM-5 : MOI (Mobil), Propylur (Lurgi), Superflex (Arco/KBR), ... 29

  30. Refinery/petrochemical integration • More naphtha fraction available for petrochemical. • Availability from refinery of additional benzene volumes. However it is not forecasted a global benzene overcapacity because of rationalization and shut-down of oldest units. • Less FCC gasoline (rich in olefins and aromatics) in the gasoline pool. • FCC will partially transform from gasoline direct supplier into intermediates producer for petrochemical (olefins) and high quality gasoline (through alkylation, etherification, …). • In general, refinery integration with petrochemicals lowers the site cost base through the exchange and optimum processing of byproduct streams. 30

  31. Crops as raw materials Since the industrial revolution, fuelled by the discovery of vast hydrocarbons reserves, the role of crops has been reduced mainly to the supply of food and feed. There are still sectors were the use of bio-resources can be significant. • Ethanol • Chemicals • Biomass gasification 31

  32. Ethanol • Organic wastes (much of this waste is crop residues) are potential low cost fermentation substrates for making ethanol. In U.S. over 97% of ethanol capacity is based on fermentation processes (2.7 billion gallons in 2003). • Largest use for ethanol, mainly in the USA and Brasil is as motor fuel. It costs much more than gasoline, but tax breaks and MTBE replacement could push its market penetration. Ethanol in petrochemical:in local and specific situations it can be employed to produce etylene via catalytic dehydration (industrial plants in India, Pakistan, Perù, for a global capacity of 60 kton/y). Strong limitations to a wider use because of its high production cost: 700-800 €/ton for ethanol vs 400-450 €/ton ethylene price 32

  33. Chemicals from crops Production of crops derived raw materials for industrial use (Mtonnes, 1999) It is unlikely that crop-derived materials will provide more than a fraction of our needs for energy or fuel. However there will be an increasing number of industrial uses for high volume/low value applications (e.g.: lubricants) or niche high added value products (agrochemicals, pharmaceuticals). 33

  34. 0.6 ha 1 ton daf biomass 1 MWh Biomass gasification The utilization potential of biomass as a fuel lies in small and medium-scale power production (<150 MWe). Biomass-fueled power generation will grow for self-generation or for local merchant generation. 34

  35. Conclusions • In the near future energy demand growth will still be satisfied mainly by fossil sources. • Non-conventional oil and gas reserves will become more important. The development of improved technologies to exploit and upgrade these sources is a key issue. • Ethylene is the main bulk chemical. Steam cracking will remain ethylene dominant production technology. No breakthrough technology expected. • New fuel quality regulation and variations in products demand will be key drivers for significant changes in refinery. This will lead to an increasing integration between refinery and petrochemical. • “Bio-sources”: their contribution can be significant in fine chemical, producing high added-value molecules. Possible massive use in biomass gasification to produce energy or bulk-chemicals (via synthesis gas). 35

  36. Upstream technology New or improved technologies are needed to exploit non-conventional resources Heavy Oils Gas Hydrates • DOE funded project to study the possibilityof producing methane hydrates from the Alaskan permafrost

  37. Steam cracking products distribution vs. feedstock (yields, % wt.) Ethylene yields decreases and co-products yield increases as the molecular weight of the feed increases

  38. Feedstock choice Investment cost varies with feedstock • Feedstock choice is related to several factors: • availability • location • feed price Major expansions are in North America, Asia (India and Far East) and Middle East. M. East will register the highest percentage growth (9.7%) in the decade 1998-2008 (mainly in S. Arabia and Iran).

  39. diffusion barrier decoking film buffer layer H2O reactor tube CO, CO2 H2 Durata del ciclo doppia rispetto al caso base. Vita più lunga dei tubi. Industrialmente applicato a tutte le fornaci di un impianto in Asia. Py-Coat (SK Corp.) Coating “on-line” ed “in-situ” dei tubi di cracking: formazione di tre strati.

  40. Fluidizized bed pyrolysis • Circulating fluid bed pyrolysis: reaction heat is carried by a solid circulating between reactor and regenerator • Advantages • Overcomes limitations due to tube materials • Feedstock flexibility (heavy feeds allowed) • No plant shut-down for decoking required Main experienxes by Chevron e Stone & Webster : TRC (Thermal Regeneration Cracking) inert solid, 500 BPD plant. QC (Quick Contact) with an active carrier: lower T, increased propylene yield Drawbacks • Low specific heat of the carrier: high circulating mass (250-300 ton/ton ethylene) • Difficult quick separation gas/solid • High erosion in reactor curves • High fine particles formation with dragging into the effluent • Complex solid dosing valves, not available commercially The need to supply high amount energy in a very short time causes strong realization problems

  41. Catalytic pyrolysis with oxides catalysts • Processo VNIIOS (Russia) • catalizzatori a base di K-vanadato/corindone o In-ossido/pomice • dimostrazione in scala semi-commerciale (7.5 ton/h) con naphtha • rese in etilene più alte e rese in propilene un po’ inferiori vs S.C. • rese in olefine ca. 10% superiori a pirolisi omogenea a T inferiore di 60-70°C Non sono annunciate realizzazioni industriali

  42. Yields (% wt.) Catalytic pyrolysis with zeolite-type cat. (1) • Catalytic Pyrolysis Process (CPP) – RIIP/Sinopec • CPP concept is an extension of the DCC process, i.e., it is an FCC process modified to increase the production of light olefins from heavy feestocks, mainly VGO and residues. Operating conditions more severe than DCC, but less than conventional steam cracking. • catalyst: modified ZSM-5 zeolite containing 2-8 wt.% P and 0.3-3 wt.% Mg or Ca • T = 650° - 700°C Results obtained with Daqing AR T = 680°C CPP technology was tested in a revamped DCC unit at Daqing Refinery (China). Outside China the process is licensed by Stone & Webster.

  43. Ethane partial oxidation Università del Minnesota Miscela etano/ossigeno/idrogeno su cat. monolitico ceramico ricoperto di Pt-Sn, riscaldato a 950°C (ignizione). Bassissimi tempi di contatto (10-3 s). Il processo è autotermico. Conversione etano: 73% Selettività ad etilene: 83% • Le prestazioni rivendicate sono superiori allo steam cracking convenzionale e gli investimenti nella fase reazione sono minori dello Steam Cracker.Sussistono però dubbi sulla fattibilità del processo: • H2 e O2 sono nel campo di esplosività • alla T di processo si ha perdita di Sn • problemi di quenching dei prodotti, dati gli alti flussi • prove di laboratorio, possibile difficoltà di scale-up

  44. Propylene production technologies:Metathesis Ethylene + 2-butenes2 propylene • 1-butene 2-butenes • tool to readjust C3=/ C2= ratio (from 0.6 to 1.1) • unit to be generally integrated with Steam Crackers • in this case, attractive economics • need of ethylene and butenes • butenes are generally available • in their absence, ethylene could be dimerized • ethylene more precious • drawback in many cases

  45. Propylene production technologies:Metathesis • OCT(Phillips/ABB Lummus) • Gas Phase Technology / tungsten oxide catalyst • old units (Phillips Petr. from C3=, Lyondell from C2=/C4=) • big plant in construction in Port Arthur (Texas) • feed from the new BASF/Fina Cracker and from Atofina refinery • Ethylene/Propylene from 920,000 / 550,000 MPTY to 830,000 / 870,000 MPTY • Meta-4(IFP) • Liquid Phase Technology / rhenium catalyst • demonstration unit in Taiwan

  46. Propylene production technologies: Propane Dehydrogenation Propanepropylene + H2 • Very specific; it gives the chance of answering selectively to the market demand of olefins • Particularly advantageous in specific cases • demand and value for propylene are both high • demand and value for propane are both low • way to locally exploit Natural Gas Liquids sources • a secure supply of propane is available • transportation costs are high • ethylene and n-butenes are not available

  47. Propylene production technologies: Propane Dehydrogenation • Different technologies available • Oleflex(UOP) • platinum catalyst / fixed bed • Catofin(ABB Lummus) • chromium catalyst / fixed bed • STAR(Phillips/Krupp Uhde) • platinum catalyst / fixed bed • FBD-3(Snamprogetti/Yarsyntez) • chromium catalyst / fluid bed • PDH (Linde/BASF) • chromium catalyst / fixed bed • High temperature operations (530-650°C) 350000 t/y propylene UOP Oleflex technology at Tarragona (Spain)

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