Haldor Topsøe Catalyzing your business

Haldor Topsøe Catalyzing your business Aldo Peiretti Chemicals General Manager Latin America Jornada sobre Gas de Síntesis y sus Derivados Instituto Petroquimico Argentino (IPA) 9 October 2013, Buenos Aires

Topsøe Group s headquarters in Lyngby, Denmark Group management Business units: Chemical, Environmental, Refinery and New Business Engineering Production Catalyst Production R&D Established 1940 Ownership: Haldor Topsøe Holding A/S (100%) Annual turnover (2012): ~700 MM EUR (~950 MM USD) Number of employees ~2300

Dr. Haldor Topsøe The corporate world in itself means nothing unless it improves the lives of people and the conditions in the poor countries "El mundo corporativo en sí mismo no significa nada a menos que mejore la vida de las personas y las condiciones en los países pobres"

Topsøe - A global supplier of catalysts and technologies Headquarters Topsøe offices Research Production Engineering Sale & Marketing Alberta Copenhagen Moscow Los Angeles Houston Bahrain New Delhi Beijing Tokyo Kuala Lumpur Rio Buenos Aires Cape Town Subsidiaries Haldor Topsoe, Inc. Haldor Topsøe International A/S, Denmark Haldor Topsoe India Pvt. Ltd. India ZAO Haldor Topsøe, Russia Subcontinent Ammonia Investment Company ApS (SAICA) Topsoe Fuel Cell A/S, Denmark

and a leading market player Market share between 15-25% for established products Supplier of solutions for 50% of new ammonia plants built within the last decade More than 60% of ammonia is produced worldwide on Topsøe catalyst Supplier for 40% of catalysts for production of ultra-low sulfur diesel > 30% market share of hydrogen catalysts Leading environmental catalysts and technologies > 35% market share of sulfuric acid catalysts 30% market share of FCC pretreatment catalysts

In short - Topsøe is dedicated to

Presentation outline Syn-Gas Technologies Conventional scheme for Ammonia / Hydrogen / Methanol Developments Benefits Ammonia & Methanol Co-production New Technologies TIGAS SNG References

Technologies Syngas technologies Ammonia Hydrogen Methanol Formaldehyde DME TREMP (SNG) TIGAS

Ammonia conventional scheme Process steam Desulphurisation Reforming Shift Natural gas Process air Stack Purge gas CO 2 - removal Ammonia product Ammonia synthesis Process Methanation cond.

Hydrogen typical flowsheet S-removal Prereformer Tubular reformer Shift PSA (pressure swing adsorption) NG LPG/ naphtha. H 2 Flue gas Combustion air BFW Fuel gas

Methanol production by one-step reforming Steam Sulphur remov. Prereformer Methanol reactor Sulphur removal Steam Makeup comp. Natural gas Steam reformer Condensate Raw methanol

Methanol production by two-step reforming Steam Sulphur sat. removal Prereformer Steam Oxygen Methanol reactor Hydrogenator Secondary reformer Steam Makeup comp. Natural gas Product methanol Steam reformer Condensate Light ends to fuel Raw methanol Water Raw methanol storage

Methanol production by ATR Oxygen/steam Autothermal reformer Methanol reactor Sulphur removal Hydrogenator Saturator Prereformer Steam Steam Natural gas Makeup comp. Rec. comp. Water Condensate Hydrogen recovery Purge gas Raw methanol

Economy of scale One-step reforming S/C ratio ~ 1.8-2.5 up to ~ 2,500 MTPD Two-step reforming S/C ratio 1.5-1.8 1,500 6,000 MTPD Autothermal reforming S/C ratio 0.6 > 5,000 MTPD. Cost Natural gas Air Natural gas Capacity Tubular reforming Oxygen plant Oxygen Air Natural gas Oxygen Syngas Syngas Syngas

Developments High flux primary reformer with Prereformer better tube materials è saving in number of tubes HTCR (Haldor Topsøe Convection Reformer) HTER (Haldor Topsøe Exchange Reformer) TBR (Topsøe Bayonet Reformer) New burner in secondary reformer New configuration on NH3 converters S-300 & S-350 Improved catalysts

Today s steam reforming technology Radiant wall reformer (SMR) 15,000-200,000 Nm 3 /h Convection reformer (HTCR) 5,000-50,000 Nm 3 /h Prereformer Exchange reformer (HTER) + 40,000 Nm 3 /h Bayonet reformer (TBR) 5,000-170,000 Nm 3 /h

Conventional scheme - prereformer Desulphurisation Reforming Prereforming (optional) Process steam Shift Natural gas Process air Stack Purge gas CO 2 - removal Ammonia product Ammonia synthesis Process Methanationcond.

Prereformer benefits Feedstock flexibility Reduced NG fuel firing Reduced steam production Reduced primary reformer size Potential for higher heat flux in primary reformer Increased run length/reliability of reformer and shift catalyst systems

HTCR - Convection Reformer gas outlet process gas outlet process gas inlet flue gas outlet Tube bundle Burner chamber flue gas inlet

The HTCR benefits High efficiency and no steam export High operating reliability Compact lay-out Short lead time

HTCR tube bundle HTCR reformer tube bundle for 27 MMSCFD unit

HTCR twinä process S-removal Prereformer HTCR twin reformer Shift PSA Steam H 2 3 x Feed Flue gas Combustion air Off-gas Fuel

HTER - Exchange Reformer Feed gas Product gas SMR effluent

Conventional scheme - HTER Desulphurisation Reforming Prereforming (optional) Process steam Shift Natural gas Process air Stack (optional) HTER Purge gas CO 2 - removal Ammonia product Ammonia synthesis Process Methanationcond.

HTER-p flowsheet Tubular reformer Secondary reformer HTER-p Process steam Desulp. natural gas Process air

HTER benefits Smaller size primary reformer Reduced NG fuel firing Reduced steam production Reduced CO 2 emissions to atmosphere ~ 10-25% reforming capacity revamp option

TBR Topsøe Bayonet Reformer Process gas outlet Process gas inlet Reformer tube Catalyst Center tube Radiant wall Radiant wall

Bayonet Reformer benefits Improvement of traditional SMR technology Low or eliminated steam export High hydrocarbon efficiency Capital cost savings Feed + fuel savings

The TBR flowsheet S-removal Prereformer Bayonet reformer Shift PSA Feed H 2 Stack Combustion air Fuel

Nozzle Burner benefits Homogeneous gas and temperature distribution at the inlet to the catalyst bed Effective mixing at the burner nozzles Low metal temperatures of the burner Less maintenance

Conventional scheme S-50 Converter Desulphurisation Reforming Prereforming (optional) Process steam Shift Natural gas Process air Stack (optional) HTER Purge gas (optional) CO 2 - removal Ammonia product Ammonia synthesis Methanation Process cond.

Conventional scheme S-50 Converter Higher conversion è higher production Higher energy efficiency Lower loop pressure Lower compressor power Higher steam generation

Recent catalyst developments TK-261 Hydrogenation High activity Low pressure drop HTZ-51 Sulphur absorbent High sulphur absorption capacity Hydrogenation activity AR-401 Prereforming catalyst Feedstock flexibility High activity

Recent catalyst developments RK-400 Reforming catalyst Alkali promotion technology Superior resistance to carbon formation LK-853 FENCE Shift catalyst Superior high and stable activity Outstanding poison resistance MK-151 FENCE Methanol synthesis catalyst Increased production & long lifetime Superior activity with lower by product level

Ammonia & Methanol Co-production Technology

Ammonia and methanol production Ammonia plant Natural gas Primary reforming Secondary reforming Co-production plant Natural gas Primary reforming Methanol plant Air separation Oxygen Secondary reforming Shift Methanol synthesis CO 2 removal Distillation Methanation Methanation Methanol Ammonia synthesis Ammonia Ammonia synthesis Ammonia Natural gas Primary reforming Autothermal reforming Methanol synthesis Distillation Methanol

Ammonia and methanol production Co-production plant Natural gas Primary reforming Secondary reforming Methanol synthesis Distillation Methanation Methanol Ammonia synthesis Ammonia Co-production plant Natural gas Primary reforming Secondary reforming Shift CO 2 removal Methanol synthesis Methanation Ammonia synthesis Ammonia Methanol

Integrated methanol, ammonia, urea plant Process steam Desulfurization Reforming Shift Oxygen Natural gas Process air Stack Purge gas Ammonia product CO2 Methanol product Ammonia synthesis Methanation Methanol synthesis CO 2 removal

Summary co-production technology Flexibility in adjustment of the ammonia and methanol production capacities Two-step reforming unit using optional enriched air in the secondary reformer Once-through methanol synthesis at standard pressure High pressure methanator Low energy consumption The simple layout increases reliability Low CO 2 emissions (reduced by ~36% from CO2 section in ammonia plant & ~20% from reformer flue gas stack if an HTER is introduced) Results in lower investment cost than individual plants Well-proven scheme with 5 plants in operation First reference has been in operation since 1993 and the latest reference plant is under construction in Russia Topsøe supplies full range of technology and catalysts

Topsøe experience list co-production plants Location Methanol capacity MTPD Ammonia capacity MTPD Start-up Middle East 72 286 1993 USA 363 600 1994 China 120 600 1999 Malaysia 200 1,125 1999 China 136 314 2003 Russia 670 1,382 2015 (exp.) Middle East 3,000 900 2015 (exp.) Middle East 3,000 900 2015 (exp.) Russia 1350 415 2016(exp.)

New Technologies

New technologies TIGAS Topsøe Integrated GAsoline Synthesis Methanol to gasoline Syngas to gasoline TREMP Topsøe REcycle Methanation Process Production of SNG (Synthetic Natural Gas)

A brief overview of the TIGAS technology Topsøe Intergrated GAsoline Synthesis Raw material for TIGAS Methanol DME Syngas The product has 88-92 octane The TIGAS product can be used directly in the gasoline pool The process has been demonstrated in large scale for 4 years

Process options for TIGAS Methanol-to-gasoline (MTG) Synthesis gas Methanol synthesis C 3 -C 4 TIGAS Gasoline Syngas-to-gasoline (STG) Water C 3 -C 4 Synthesis gas MeOH/DME synthesis TIGAS Gasoline Water

A brief overview of the TREMP technology SNG generated by methanation of syngas CO + 3H 2 CH 4 + H 2 O CO 2 + 4H 4 CH 4 + 2H 2 O Typical raw material for the syngas biomass, waste, coal, petcoke Markets for SNG Where NG resources limited Where the raw materials are abundant Strategic energy sourcing

First modern SNG plant Largest single train SNG plant 1.4 billion Nm 3 /year Contract awarded in September 2009 Contract includes: Licence Engineering Catalyst Services Procurement assistance Start-up in autumn 2013 Xinjiang Qinghua Coal Based Co. Ltd. in China

Principales clientes en America Latina PETROBRAS (ULSD, Hidrógeno, WSA/SNOX, Amoniaco) - Refinerias RNEST, REFAP, REVAP, REGAP, REDUC, UFN-5, etc. PEMEX (8 nuevas unidades ULSD, Hidrógeno, Amoníaco) PDVSA (Petropiar, Petrocedeño, Amuay, Cardon) PEQUIVEN (FertiNitro, Metor, SuperMetanol, Morón, El Tablazo) YPF (Lujan de Cuyo: ULSD, Hidrógeno, WSA Huincul: Metanol) PETROPERU (Refinería Talara: ULSD, Hidrógeno y WSA) PROFERTIL (Amoniaco) ENAP (Refineria BioBio y Aconcagua, catalizadores para Hidrocraqueo) STAATSOLIE, Suriname (Hidrógeno y WSA) ANCAP (ULSD) MOLYMET (WSA) CUVEMPEQ (Amoníaco)

Haldor Topsøe en Argentina PROFERTIL, Bahia Blanca Planta de amoniaco, 2,000 mtpd AIR LIQUIDE, Campana Planta de Hidrogeno, 15,000 Nm3/h ENSI Planta de Agua Pesada, Neuquen Sintesis de NH3 y crackers de NH3 YPF Refineria Lujan de Cuyo Planta de Hidrogeno, 6,000 Nm3/h YPF Planta de Metanol, Plaza Huincul - Catalizadores Metanol YPF Refineria Lujan de Cuyo, Internos Rxs y catalizadores de Hidrotratamiento - Catalizadores hidrocraqueo ISOMAX - Reactor Design Package & Internos Rxs & catalizadores para Unidad HDS-3 Catalizadores planta de hidrogeno BEDP para planta WSA YPF Refineria La Plata Internos Rxs HTG Hidrotratamiento de gas oil BEDP para planta WSA Axion Energy, Campana NHT catalysts Bunge, Campana Catalizadores para planta de amoniaco Alto Paraná, San Martin Catalizadores para la Sintesis de Metanol Catalizadores para Acido Sulfurico en DGFM / Meranol / Akzo Nobel

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