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 ¡ Established 1940
– Business units: Chemical, ¡ Ownership: Haldor Topsøe Holding A/S
Environmental, Refinery and (100%)
New Business ¡ Annual turnover (2012): ~700 MM EUR
– Engineering Production (~950 MM USD)
– Catalyst Production
– R&D
¡ 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

Copenhagen Moscow
Alberta

Beijing
Tokyo
Los Angeles Houston Bahrain
New Delhi

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
Desulphurisation Reforming Shift

Process steam

Natural gas

Process air
Stack

Purge gas
CO2-
removal

Ammonia Process
product Ammonia synthesis Methanation cond.
 Hydrogen typical flowsheet
Pre- Tubular PSA
S-removal Shift
reformer reformer (pressure
swing
adsorption)

NG

LPG/
naphtha.
H2

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 Steam reformer

gas

Condensate

Raw methanol
 Methanol production by two-step reforming
Steam Oxygen
Sulphur sat. removal
Steam
Pre- Methanol
reformer reactor

Secondary
Hydrogenator reformer

Steam
Makeup
comp.

Natural Steam reformer

gas
Condensate
Light ends to fuel Raw
Product
methanol
methanol

Water Raw methanol storage

 Methanol production by ATR
Autothermal Methanol
Oxygen/steam reformer reactor
Steam Steam
Hydro- Sulphur Saturator Pre-
genator removal reformer

Natural gas

Makeup
comp.

Rec.
comp.
Water Condensate
Purge
Hydrogen
recovery gas

Raw methanol
Economy of scale
¡ One-step reforming
– S/C ratio ~ 1.8 - 2.5

Cost
– up to ~ 2,500 MTPD
Tubular reforming
¡ Two-step reforming Oxygen plant

– S/C ratio 1.5 - 1.8 Capacity

– 1,500 – 6,000 MTPD Oxygen Oxygen
Air Air

Natural Natural Natural

¡ Autothermal reforming gas gas gas

– S/C ratio 0.6

– > 5,000 MTPD.
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) Convection reformer (HTCR)
15,000-200,000 Nm3/h 5,000-50,000 Nm3/h

Prereformer

Exchange reformer (HTER) Bayonet reformer (TBR)

+ ≤40,000 Nm3/h 5,000-170,000 Nm3/h
 Conventional scheme - prereformer
Desulphurisation Reforming Shift
Prereforming (optional)
Process steam

Natural gas

Process air
Stack

Purge gas
CO2-
removal

Ammonia Process
product Ammonia synthesis 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
process gas outlet
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

H2
Steam
3x

Feed
Combustion air

Flue gas Off-gas

Fuel
 HTER - Exchange Reformer
Feed gas

Product gas

SMR effluent
 Conventional scheme - HTER
Desulphurisation Reforming Shift
Prereforming (optional)
Process steam

Natural gas
(optional)
Process air HTER

Stack

Purge gas
CO2-
removal

Ammonia Process
product Ammonia synthesis 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 CO2 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 Pre- Bayonet Shift PSA
reformer reformer

H2
Feed

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 Shift
Prereforming (optional)
Process steam

Natural gas
(optional)
Process air HTER

Stack

Purge gas
(optional) CO2-
removal

Ammonia Process
product Ammonia synthesis Methanationcond.
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

Shift catalyst
LK-853 FENCE
¡ 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 Secondary Ammonia Ammonia
Co-production plant
reforming reforming
Shift CO2 removal Methanation
synthesis
Methanol
Distillation
Natural
gas Primary Secondary Methanol
Methanol plant
reforming reforming synthesis
Ammonia
Ammonia
Methanation
synthesis
Air Oxygen
separation

Natural
gas Primary Autothermal Methanol Methanol
Distillation
reforming reforming synthesis
 Ammonia and methanol production

Co-production plant
Methanol
Distillation
Natural
gas Primary Secondary Methanol
reforming reforming synthesis
Ammonia Ammonia
Methanation
synthesis

Co-production plant
Natural
gas Primary Secondary
Shift CO2 removal
reforming reforming

Methanol Ammonia Ammonia

Methanation
synthesis synthesis

Methanol
 Integrated methanol, ammonia, urea plant
Desulfurization Reforming Shift
Process steam Oxygen

Natural gas

Process air

Stack
Purge gas

Ammonia CO2
product
Methanol product Ammonia synthesis Methanation Methanol synthesis CO2 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 CO2 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 Ammonia capacity Start-up
MTPD MTPD
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

C3-C4

TIGAS

Gasoline

Water

¡ Syngas-to-gasoline (STG)

C3-C4
Synthesis gas
MeOH/DME TIGAS
synthesis
Gasoline

Water
A brief overview of the TREMP technology
¡ SNG generated by methanation
of syngas
– CO + 3H2 → CH4 + H2O
– CO2 + 4H4 → CH4 + 2H2O
¡ 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 Nm3/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
Gracias por su atención