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Petrochemical Industry: Role of Innovations and Feedstock Availability
Bipin VoraConsultant, Former UOP Fellow
Lecture organised by PetroFedand
Lovraj Kumar Memorial Trust
AtIndianOil Institute of Petroleum Management,
Gurgaon, India on March 6, 2008
Vora International Process (VIP) Corp
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Outline Introduction Technology
Innovations and Feedstocks Coal & Natural Gas Aromatics Olefins
SummaryVora International Process (VIP) Corp
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PetrochemicalsPetrochemicalsThere are three basic raw materials that make up major part of Petrochemical industry
1. Synthesis Gas from Coal or Natural GasHydrogen, Ammonia, Urea, Methanol, GTL/CTL and derivatives
2. AromaticsBenzene, Toluene and Xylenes (BTX) and its derivatives
3. OlefinsEthylene, Propylene and its derivatives
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Outline Introduction Technology
Innovations and Feedstocks Coal & Natural Gas Aromatics Olefins
Summary
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Petrochemicals:MethanePetrochemicals:Methane DerivativesDerivatives
CoalCoal Gasification
NaturalGas
LNG
FT
Methanol
Synthesis Gas
MTO
Ethylene Propylene
GTL Fuel
Fuel
Fuel
Electricity
Steam
Reforming, Partial Ox. MTG
Liquid Fuel
Hydrogen Ammonia Urea
Formaldehyde Acetic acid MTBE & Other Chemicals
DME Fuel
Vora International Process (VIP) Corp
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Coal & Natural Gas New investments and
production for some products shifting where lower cost natural Gas is available
With high crude oil prices Coal is coming back
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Alternative Feedstocks for petrochemicals and polymersVol. 2, Issue 2 January 28,2008, A weekly publication
1. PT Bumi Resources interested coal liquification plant in Indonesia
2. Reliance Industries interested in CTL plant in India3. Gail planning coal project in China4. Yankuang Groups CTL plant approved in China5. China Coal to fund chemical projects from IPO6. Sasol plans to build indirect CTL plant in China7. Malaysia plans integrated gas-petrochemical project8. Itera and Uralkhimpst to build 600 KTA methanol plant
in Rusiia9. Shell proposes LNG/GTL project in Egypt10. Mitsubishi gas Chemical kicks off 850 kta methanol
plant in China11. Dow invests in direct methane utilization technology
There are 5 to 10 weekly news items on coal and natural gas upgrading
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Synthesis Gas :Synthesis Gas :-- Key to Conversion of Key to Conversion of Natural gas or CoalNatural gas or Coal
For Coal or natural For Coal or natural gas to chemicals, gas to chemicals, synthesis gas is the synthesis gas is the key intermediatekey intermediate
With continuous With continuous incremental incremental improvements, basic improvements, basic technology is technology is unchangedunchanged
Natural GasNatural GasCoal
Steam Reforming,Partial Ox
Synthesis Gas
LNGElectricity
Gasification
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Synthesis Gas :Synthesis Gas :-- Key to Conversion of Key to Conversion of Natural gas or CoalNatural gas or Coal
Synthesis Gas
Methanol
Fisher-Tropsch
GTL
DME
MTO Ethylene, Propylene
MTG Gasoline
Acetic Acid Formaldehyde
MTBE Chemicals
Fuel
Hydrogen Ammonia
Urea
Linear paraffins
Wax
Liquid Fuel
Fuel
UOP 4628I-34
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Coal & Natural gas (Methane)Coal & Natural gas (Methane)
Pre-1950s Coal based petrochemicals
In 1955 US Benzene production 70 % from Coal and 30% from Petroleum
Late 1950s - With Refining capacity increasing and development of catalytic reforming technology, naphtha becomes primary feedstock
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Methanol Plant ConstructionMethanol Plant Construction1980s1980s 1990s1990s 20002000--20082008
NANA--USA & CanadaUSA & Canada VenezuelaVenezuela Trinidad & TobagoTrinidad & TobagoRussiaRussia--SiberiaSiberia NorwayNorway ChileChileSaudi ArabiaSaudi Arabia IranIran IranIranMalaysiaMalaysia Qatar, Qatar, QatarQatarUkraineUkraine Saudi ArabiaSaudi Arabia OmanOman
IndonesiaIndonesia
LibyaLibya TrinidadTrinidad ChinaChina--CoalCoalNew ZealandNew Zealand LibyaLibyaIndonesiaIndonesia ChileChile
MalaysiaMalaysia
Pre 1980 production mostly in NA, WE and Japan Post 1980 new Construction mostly at advantaged natural gas sites
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MethanolMethanol--SummarySummary Industry shifted to locations where cost
of natural gas is lower
Single train production capacity increased from 2500 MTD to 5000 MTD, lowering cost of production per ton of methanol
One or more new plants under design construction with capacity of up to 10000 MTD
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Outline Introduction Technology
Innovations and Feedstocks Coal & Natural Gas Aromatics Olefins
Summary
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Aromatics (BTX): Raw Material &TechnologyAromatics (BTX): Raw Material &Technology 1950s: Development of liquid-liquid solvent
extraction technology accelerates production and uses of BTX
1952 Extraction by EG; Dow Chemical 1960s Extraction by Sulfolane; Shell
1960s: Adsorptive separation of components, employing molecular sieves, by class and molecular shape developed
1964: separation of normal paraffins from kerosene accelerated production of linear alkylbenzene (LAB)
Until 1970 paraxylene produced via Crystallization 1971 Adsorptive Separation, UOP Parex
Commercialized for pX production
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Petrochemicals:BTXPetrochemicals:BTX DerivativesDerivativesBenzeneBenzene
2007: 38 mm MTA2007: 38 mm MTATolueneToluene
2007: 36 mm MTA2007: 36 mm MTAXyleneXylene
2007: 33 mm MTA 2007: 33 mm MTA EBEB--StyreneStyrene Toluene Toluene diisocynatediisocynate pXpX--PTAPTA--PolyesterPolyester
CumeneCumene--PhenolPhenol--PhenolicPhenolic resinsresins
Motor FuelMotor Fuel--Octane Octane EnhancementEnhancement
oXoX--PhathalicPhathalic anhydrideanhydride
LABLAB SolventSolvent mXmX--isophthalicisophthalic acidacid
CyclohexaneCyclohexane Conversion to Conversion to BzBz--pXpX
CyclohexnolCyclohexnolCyclohexanoneCyclohexanone
oX/mXoX/mX Conversion to Conversion to pXpX
CaprolectumCaprolectum--NylonNylon
AdipicacidAdipicacid--NylonNylon
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Aromatics (BTX)Aromatics (BTX)
Pre-1950s Coal based petrochemicals In 1955 US Benzene production 70 % from
Coal and 30% from Petroleum
1950s - With Refining capacity increasing and development of catalytic reforming technology, naphtha becomes primary feedstock
Two ways of deriving aromatics from naphtha
Naphtha reforming Pyrolysis of Naphtha
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Crystallizer Capacity
Parex
02468
1012141618202224
C
a
p
a
c
i
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y
,
M
T
A
(
m
i
l
l
i
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n
s
)
1970 1975 1980 1985 1990 1995 2000
.
CrystallizationOther
Increasing market share by adsorptive Increasing market share by adsorptive separation technologyseparation technology
Worldwide Worldwide pp--Xylene Production CapacityXylene Production Capacity
Source: UOP
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UOP UOP ParexParexRR UnitsUnitsIncreasing single train production CapacityIncreasing single train production Capacity
00
200200
400400
600600
800800
10001000
12001200
14001400
19701970 19751975 19801980 19851985 19901990 19951995 20002000 20052005
p
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X
y
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e
,
K
M
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X
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K
M
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20102010
Parex Units Under ConstructionParex Units Under ConstructionParex Units On-StreamParex Units On-Stream
November 2006November 2006
yy 77 Parex units had been brought on stream77 Parex units had been brought on streamyy 14 Parex units under construction14 Parex units under construction
Source: UOP
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BenzeneBenzene-- ParaxyleneParaxyleneSummarySummary
Sulfolane continues to be preferred solvent for aromatics extraction
Adsorptive separation is preferred technology for paraxylene
No radical shift foreseen in use of raw material or technology, Naphtha remains dominant raw material
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Linear Linear AlkylbenzeneAlkylbenzene (LAB)(LAB)3.3 mm MTA production in 20073.3 mm MTA production in 2007
Kerosene n- paraffins Adsorptive separation
n-paraffins linear olefins + H2 Catalytic dehydrogenation
Linear olefins + Benzene LAB HF Acid or Solid acid Catalysis
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Continuous Renewal of LAB TechnologiesContinuous Renewal of LAB Technologies
0
500
1,000
1,500
2,000
2,500
3,000
3,500
4,000
1965 1970 1975 1980 1985 1990 1995 2000 2005Year
C
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,
K
M
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UOP DetalUOP HFOther AlCl3/HFDDB
Source: UOP
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Linear Linear AlkylbenzeneAlkylbenzene (LAB)(LAB)SummarySummary
Use of DDB began in 1940s, though superior in detergency, it is phased out due to poor biodegradability
All future growth of LAB is expected to use alkylation technology employing solid acid catalyst
Kerosene based paraffins may face competition from GTL based paraffins in future
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Outline Introduction Technology
Innovations and Feedstocks Coal & Natural Gas Aromatics Olefins
Summary
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Petrochemicals:OlefinsPetrochemicals:Olefins DerivativesDerivatives
EthyleneEthylene2007: 120 mm MTA2007: 120 mm MTA
PropylenePropylene2007: 70 mm MTA2007: 70 mm MTA
ButadieneButadiene2007: 10 mm MTA 2007: 10 mm MTA
PolyethylenePolyethylene PolypropylenePolypropylene Polymers and copolymers Polymers and copolymers with styrene and ACNwith styrene and ACN
EBEB--StyreneStyrene AcrylonitrileAcrylonitrile ABSABS
Ethylene OxideEthylene Oxide--Ethylene glycols,Ethylene glycols,
CumeneCumene--PhenolPhenol nButenenButene--MEKMEK
EDC, VCMEDC, VCM Propylene OxidePropylene Oxide IsobuteneIsobutene--TBATBA
Vinyl acetateVinyl acetate EpichlorohydrinEpichlorohydrin, , GlycerolGlycerol
DiisobuteneDiisobutene, , triisobutenetriisobutene& & polyisobutenepolyisobutene
Ethyl alcoholEthyl alcoholacetaldehydeacetaldehyde
NonylphenolNonylphenolTetramerTetramer
IsobuteneIsobutene--MTBEMTBE
Motor Fuel Motor Fuel AlkylateAlkylate
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Ethylene: Ethylene: Raw Material &TechnologyRaw Material &TechnologyRaw Materials Technology EthanePropane, butane Thermal PyrolysisNaphtha, gas oil
Incremental innovations in thermal cracking and furnace design technology have allowed single train ethylene capacity to exceed 1 mm MT/Yr
Natural gas based or coal based Methanol toOlefins technology is on horizon
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EthyleneEthylene Until 1980 primary production in NA, WE and Japan
Choice of feedstock depended on region Feedstock USA WE JapanYear 79 91 06 79 91 79 91C2-C4 65 75 70 4 8 10 2Naphtha-GO 35 25 30 96 92 90 98
NA more ethane based WE and Japan Naphtha based
Expansion of ethylene production in ME promotes more ethane based crackers
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Middle east Ethylene CapacityMiddle east Ethylene CapacityYearYear MTAMTA20002000 7720042004 111120082008 181820122012 3535
Source: CMAI- 2007 World Petroch. Conf.
Ethylene produced from Ethane in ME has on average 250 to 400 $/MT production cost advantage over NA/WE Europe production
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Ethylene Supply Ethylene Supply Global ViewGlobal View
Gas Oil5%
Others2%
Propane
8% Butane
4%
Ethane29%
Naphtha
52%
Gas Oil5%
Others2%
Propane
8% Butane
4%
Ethane29%
Naphtha
52%
2006 Supply2006 Supply(Steam Crackers)(Steam Crackers)
Incremental Supply
100
120
140
160
180
2
0
0
6
2
0
0
8
2
0
1
0
2
0
1
2
2
0
1
4
m
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M
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A
Non-ethaneEthaneCurrent BaseDemand
Incremental Supply
100
120
140
160
180
2
0
0
6
2
0
0
8
2
0
1
0
2
0
1
2
2
0
1
4
m
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Non-ethaneEthaneCurrent BaseDemand
Source: CMAI 2007Source: CMAI 2007
47%
UOP 4585F-04
53%
Production from ethane crackers will increase Non-ethane sources of ethylene are needed to
meet the demand
Production from ethane crackers will increaseProduction from ethane crackers will increase NonNon--ethane sources of ethylene are needed to ethane sources of ethylene are needed to
meet the demandmeet the demand
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Other2%PDH3%
Metath.2%
OC0.3%
FCC31%
Steam Crackers
62%
Propylene Supply Propylene Supply Global ViewGlobal View2006 Supply2006 Supply
(Polymer & Chemical Grades(Polymer & Chemical Grades)
Source: CMAI 2007Source: CMAI 2007
Incremental Supply
60
70
80
90
100
110
2
0
0
6
2
0
0
8
2
0
1
0
2
0
1
2
2
0
1
4
m
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On-purpose propyleneFCC RefineriesSteam CrackersCurrent BaseDemand
42%
14%43%
Substantially more propylene will come from on-purpose propylene technologies
Substantially more propylene will come from Substantially more propylene will come from onon--purpose propylenepurpose propylene technologiestechnologies
PDH = Propane Dehydrogenation, Metath. = Metathesis, OC = Olefin Cracking, MTO = Methanol-to-Olefins
On-purpose propylene = PDH + Metath. + OC + MTOUOP 4585F-05
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PDH Capacity GrowthPDH Capacity Growth
0.0
1.0
2.0
3.0
4.0
5.0
1990 1994 1998 2002 2006 2010
C
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0
100
200
300
400
500
600
U
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k
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Installed CapacitySize of New Units
0.0
1.0
2.0
3.0
4.0
5.0
1990 1994 1998 2002 2006 2010
C
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M
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A
0
100
200
300
400
500
600
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Installed CapacitySize of New Units
UOP 4824D-06
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ZeoliteZeolite--catalyzed catalyzed MeOHMeOH conversionconversion
1975 1975 Mobil Oil discloses ZSMMobil Oil discloses ZSM--5 catalyst for 5 catalyst for conversion of methanol to gasoline (MTG)conversion of methanol to gasoline (MTG)
2 CH3OH CH3-O-CH3-H2O
+H2O-H2O
IsoparaffinsAromaticsC6+ olefins
C2 - C5 olefins
Chang, Silvestri, and Smith, US 3894103 and 3928483
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ZeoliteZeolite--catalyzed catalyzed MeOHMeOH conversionconversion
1977 1977 Mobil Oil discloses the use of various Mobil Oil discloses the use of various small pore small pore zeoliteszeolites for converting methanol to for converting methanol to olefins (MTO)olefins (MTO) CC22CC44 olefin concentration < 60% at 100% conversionolefin concentration < 60% at 100% conversion
Olefin fraction increases as conversion decreasesOlefin fraction increases as conversion decreases
Chang, Lang, and Silvestri, US 4062905
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ZeoliteZeolite--catalyzed catalyzed MeOHMeOH conversionconversion 1982 1982 Edie Edie FlanigenFlanigen and her associates at and her associates at
Union Carbide announce discovery of Union Carbide announce discovery of silicosilicoaluminum aluminum phospatephospate molecular sieves. molecular sieves. FlanigenFlanigenand her group became part of UOP upon and her group became part of UOP upon merger of CAPS Division of UCC with UOPmerger of CAPS Division of UCC with UOP
SAPOSAPO--34 shows remarkable selectivity for 34 shows remarkable selectivity for conversion of methanol to light olefinsconversion of methanol to light olefins
CC22CC44 olefin concentration < 85% at 100% olefin concentration < 85% at 100% conversionconversion
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Structures of SAPOStructures of SAPO--34 and ZSM34 and ZSM--55
H O
(Al-O)3Si Al(O-P)3
H O
(Al-O)3Si Al(O-P)3
H O
(Si/Al-O)3Si Al(O-Si)3
H O
(Si/Al-O)3Si Al(O-Si)3
Small PoreWeak Acid Sites
Medium PoreStrong Acid Sites
3.8 5.5
Source: UOP
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Product Yields from Product Yields from MeOHMeOH::SAPOSAPO--34 and ZSM34 and ZSM--5 Catalysts5 Catalysts
0
10
20
30
40
50%
Y
i
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l
d
C2= C3= C4= C5+ C1-C5Paraffins
Coke +COx
SAPO-34ZSM-5
SAPO-34 Catalyst: Once through C2= + C3= yield of 80%ZSM-5 Catalyst: Once through C2= + C3= yield of 50%
Source: UOP
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MTO Capacity GrowthMTO Capacity Growth
0.0
1.0
2.0
3.0
4.0
5.0
1996 2000 2004 2008 2012
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0
200
400
600
800
1000
1200
1400
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Installed CapacitySize of New Units
0.0
1.0
2.0
3.0
4.0
5.0
1996 2000 2004 2008 2012
C
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0
200
400
600
800
1000
1200
1400
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Installed CapacitySize of New Units
UOP 4824D-06
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Patent Activity in USA
Syngas Conversion
0102030405060708090
100
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
Year
#
U
S
P
a
t
e
n
t
s
Syngas to MeOHSyngas to C2+ alcoholSyngas to FT LiquidMTO + MTG
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EthyleneEthylene--PropylenePropyleneSummarySummary
ME becomes a major player: China, India growing as well
Advantaged ethane supply in ME is limited Coal or natural gas based Methanol will be a new
raw material source for ethylene and propylene Naphtha cracker and refinery FCC units will
continue to be major source for propylene Advantaged propane feed stock will promote
PDH at selective locations In future, natural gas based MTO projects at
advantaged NG locations (ME, USSR..) may give tough competition to naphtha based projects.
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Value of Products Produced from Value of Products Produced from 1MM BTU of Natural Gas1MM BTU of Natural Gas
0
2
4
6
8
10
12
Natural Gas
LNG Gasoline Methanol Olefins Polymers
V
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o
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P
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s
,
$
Minimum of $4 per mmBTU differential is needed for NG to delivered LNG
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Stranded Gas Monetization Options(for world-scale capacities with $ 2 to 6 billion
investment)30 Years
Consumptionbillion SCM
Worldscaleeconomic capacity
Gas neededmm SCMD
Monetizationroute
5 MM MTALNG 22.2 222LNG
100,000 BPDF-T LiquidsGTL 26.8 268
1,000,000 MTAPE + PPGTP 7.5 75
LNG and GTL are suitable for only the largest gas fieldsGTP can be implemented on many more gas fields
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WorldWorlds gas fields by sizes gas fields by size
Number of Fields0%
10%20%30%40%50%60%70%80%90%
100%%
o
f
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d
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a
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f
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50 - 500 Tcf5-50 Tcf1 - 5 Tcf0.5 - 1 Tcf0.25 - 0.5 Tcf0.1 - 0.25 Tcf0.01 - 0.1 Tcf< 0.01 Tcf
Large Fields =13%
Total = 4,448 Fields Source: Oil & Gas Journal
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Why is Methanol Attractive?Why is Methanol Attractive? Readily synthesized on a large Readily synthesized on a large
scale (current largest unit is 5000 scale (current largest unit is 5000 MTD, 10,000 MTD under design)MTD, 10,000 MTD under design) Transportable liquid fuelTransportable liquid fuel Has high energy densityHas high energy density
HH2 2 gasgas
Methane Methane gasgas
DME DME gasgas
Methanol Methanol liquidliquid
Naphtha Naphtha liquidliquid
3.97x103.97x1066 8.2x108.2x1066142001420024002400Kcal/MKcal/M33
@ 1 atm. @ 1 atm. 25C25C
86008600
LNG Transportation Cost about $150-200MTMethanol Transportation Cost $10-20/MT
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Advances in Methanol TechnologyAdvances in Methanol Technology Significant advances Significant advances
have taken place in have taken place in mega methanol mega methanol projectsprojectsFirst 5000 MTD First 5000 MTD methanol plant in methanol plant in operation in Trinidad operation in Trinidad since July 2004since July 20047500 MTD plant for 7500 MTD plant for Nigeria in designNigeria in design10 to 15000 MTD 10 to 15000 MTD plants for Qatar in plants for Qatar in planningplanning
Cost of methanol Cost of methanol production has come production has come down significantlydown significantly
100 $/MT MeOH = 229 $/MT HC Equiv.150 $/MT MeOH = 343 $/MT HC Equiv.
0
50
100
150
200
250
300
Industrial location
Stranded gas location
Mega-scalemethanol
Mega-scaleMethanol
Shipping15% ROCDepreciationFixed costsConsumablesNat. gas
C
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,
$
/
M
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a
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0
50
100
150
200
250
300
Industrial location
Stranded gas location
Mega-scalemethanol
Mega-scaleMethanol
Shipping15% ROCDepreciationFixed costsConsumablesNat. gas
C
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t
,
$
/
M
T
m
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a
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Nat. gas Price, $/MM Btu $5.00 $0.75 $0.50 $2.00Capacity, MT/D 1500 3000 7500 7500
269
121
85
136
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Methanol Plant Closure
19901990--20042004 20052005--2007 Closure2007 Closure
Japan 100%Japan 100% Beaumont, USA 850Beaumont, USA 850
Norway 100%Norway 100% Celanese, Bishop, USA 500Celanese, Bishop, USA 500
Korea 100%Korea 100% Celanese, Clear Lake, USA 600Celanese, Clear Lake, USA 600Italy 100%Italy 100% MethanexMethanex, , KitimatKitimat, Canada 520, Canada 520
Spain 100%Spain 100% Edmonton, Canada 800Edmonton, Canada 800
France 100%France 100% PemexPemex, Mexico 180, Mexico 180USA Part of itUSA Part of it MethanorMethanor, Netherland 1000, Netherland 1000
Canada Part of itCanada Part of it MethanexMethanex, New Zealand , New Zealand 700700Total 5150Total 5150
Source: 2007 CMAI World Methanol Conf.
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Why is Methanol Attractive?Why is Methanol Attractive?
NG to LNG Delivered C efficiency about 85-90%
NG to Methanol C efficiency about 70-80%
LNG Transportation Cost about $150-200MT
Methanol Transportation Cost $10-20/MT
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Gas to Polymer/Olefin ScenariosGas to Polymer/Olefin Scenarios
Polyolefin Markets
Remote Gas Production
Methanol PlantMTO Plant
Polyolefin Plant
Integrated GTPMethanol Plant
MTO PlantPolyolefin Plant
Segregated GTP
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Patent Activity in USA
Syngas Conversion
0102030405060708090
100
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
Year
#
U
S
P
a
t
e
n
t
s
Syngas to MeOHSyngas to C2+ alcoholSyngas to FT LiquidMTO + MTG
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Overall SummaryOverall Summary
New application for production of light olefins will accelerate growth
Significant Patent activity for Methanol to Olefins
Though research continues in direct conversion of methane, no breakthrough on horizon
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Overall SummaryOverall Summary Time and time again, technology breakthrough has made
major impact on industry.
Industry always looks at availability of lower cost raw material or shifts to where they are
No major changes expected in BTX or LAB production technologies
As happened to the methanol industry, Olefins industry is poised for another change to come
Natural gas based ethylene and propylene via MTO will dominate future new capacity
Methanol will become a bigger and more important industry
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AcknowledgementAcknowledgement
My thanks to UOP and UOP colleagues for providing me updates on UOP processes
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