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Mr. Joseph C. Gentry
Director, Global LicensingGTC Technology US, LLCUSA
Mr. Joseph earned a BS degree in chemical engineering from AuburnUniversity and an MBA from the University of Houston. He is theinventor of several patented separations technologies and hasspecialized in the application of these for the petrochemical industry.
He has previously worked for ARCO Chemical Company, and LyondellPetrochemical Company as a process engineer in the olefins andaromatics areas and has authored several papers on licensing processtechnologies in refining and petrochemical applications.
He is a specialist in GT-BTX and GT-Styrene, working in all areas ofTechnology, Licensing and Business Development.
Unlocking Value Potential from Naphtha CrackerBy-Product StreamsJoseph C. Gentry • Director, Global Licensing
IOCL 2013 Petrochemical Conclave March 18, 2013
Introduction to GTC TechnologyIntroduction to GTC Technology
• Technology and global licensor for • Regional subsidiaries in China, Korea, innovative solutions in:
– Petrochemicals – Chemicals
India, Singapore, the Czech Republic and Mexico
S ti d M T f S l ti– Refining– Gas processing/Sulfur
• Separations and Mass Transfer Solutions
• Process know-how, engineering, equipment, critical chemicals/catalysts and services
Page 2
• Global headquarters - Houston, Texas critical chemicals/catalysts and services
Naphtha Based Steam Cracker Operators - Increased global competition
“I used to do pretty well just focusing on ethylene and propylene.
“Now I have to recover as many ofthe heavier co-products as I can to stay competitive globallystay competitive globally.
“Increased competition from producers with cost advantaged feedstock andwith cost advantaged feedstock and shale gas ethane in North America has not helped.
Fortunately my naphtha cracker makes some higher value products in the Py-gas stream.
I wonder if I can separate and market them?”
Searching for added value in C5 –C12 P f th k
Page 3
Py-gas from the cracker
Typical Product Slate from Naphtha CrackerTypical Product Slate from Naphtha Cracker
FeedstockProduct
Feedstock
Ethane Propane Butane Naphtha Atmospheric Gas Oil
Vacuum Gas Oil
9 % 9 2 2 2 1 1Hydrogen - 95% 9 2 2 2 1 1
Methane 7 28 22 17 11 9
Ethylene 78 42 40 34 26 21
Propylene 2 17 17 16 16 14
Butadiene 1 3 4 5 5 5
Pyrolysis Gasoline, 1 7 7 19 18 19y y ,including:
PiperyleneCyclopentadiene
Isoprene
---
---
---
0.31.40.9
1 22
1 2.52p
BenzeneToluene
XyleneStyrene
10--
31--
31--
7311
6311
43
0.80.8Styrene
Other, C9+ 0 3 116
12
0.80
Fuel Oil 0 1 2 5 18 25Balance 0 0 6 11 5 6
Page 4
* Values obtained at high severity and with recycling unconverted E/P Stream, Chauvel & Lefebvre 1989
GTC Portfolio in Refining, Petrochemical, Gas Processing/Sulfur & Polyester Industries
C5 Processing
Disproportionation
IsoprenePiperyleneDCPD, HCR
Benzene
GTC Licensed Technology
Natural Gas
SteamCracker
PetrochemicalComplex
Aromatization
StyreneRecovery
p p
Alkylation
Transalkylation
Heavy Olefins
StyrenePyrolysis Gasoline
Benzene, TolueneXylene (BTX)
MeOH
NGL
ComplexParaxyleneRecovery
Crystallization/Hybrid
NaphthaleneResin Oil
PGOProcessingSulfur
Hydrotreating
NaphthaReforming
Hydrotreating Isomerization
BTXRecovery
BenzeneDX
Process
IsomerizationLightNaphtha
HeavyNaphtha
BenzeneToluene
Crude OilXylenes
Fuel
still
atio
n
Saturation
Aromatization
Process Kerosene
Gasoil Fuel
C4/C5
HeavyAromatics
Fuel
ParaxyleneDesulfurization
PTAEG
Cru
de D
is
Fuel
FCCU
GT-BTX PluS®
FCCNaphtha
Residue
DMT(DMI)
MeltPhase
Polyester
(IPA)PolyesterChip
SulfurSulfur Recovery Unit
Page 5
Residue
Unlocking Value in the Py-gas Streamfrom every carbon molecule, C5-C12
C5 Di l fiC5 – Diolefins
• Piperylene (1,3 pentadiene) “Pip’s” → Hydrocarbon Resin “HCR”
• DCPD → HCR, Unsaturated Polyester ResinC C , U sa u a ed o yes e es
• Isoprene → Rubber
C6 - Benzene → EB → StyreneC6 Benzene → EB → Styrene
C7 – Toluene
• XylenesXylenes
• Toluene (Methylation with MeOH) → Paraxylene
C8 – Xylenes → Paraxylene → PTA → PolyesterC8 y e es a a y e e o yeste
• Styrene (Extraction) → SBR, PS, Rubber
C9 – Resin Oil → HCR → Inks, AdhesivesC9 Resin Oil HCR Inks, Adhesives
C10 – Naphthalene → Naphthenic Derivatives
C11 C12 Aromatic Sol entsC11–C12 – Aromatic Solvents
Page 6
2012 Global Ethylene Cash Costs2012 Global Ethylene Cash Costs
(Dollars per Ton)
1450
1650(Dollars per Ton)
1250
1450
West Europe Avg.NE Asia Avg.
850
1050
$ Co‐Product Recovery Impact0
50100150
SE Asia Avg.
450
650150
U.S. AverageMDE Avg.
Alberta Ethane
U.S. EthaneMDE
Ethane250
450
Alberta Ethane500 20 40 60 80 100 120 140 160
CUMULATIVE ETHYLENE CAPACITY (million tons)
Data provided courtesy of IHS/CMAI
Economical Ethylene Capacity for Recovering By-products
, Secondary Deriv.
Isoprene DCPD PipsProd
uce
Naphthalene, Secondary Deriv.
Butadiene, Benzene, Toluene, Xylenes
Styrene Extraction, C9 Resins
Isoprene, DCPD, Pips
mic
al to
P
Ethylene, Propylene, Primary Derivations
Butadiene, Benzene, Toluene, Xylenes
Econ
om
Ethylene rate, KTA
200 1400400 600 800 1000 1200
Ethylene rate, KTA
(Liquids feed)
Primary By-products from PygasPrimary By-products from Pygas
Isopentane
High-purity Isoprene99 wt %
C5 to recycle crackingIsopentane
Crude Isoprene
High-Purity
99 wt. %
Piperylenes
Extraction Isoprene
High-Purity
C5 Fraction
RawPyrolysis Gasoline
High-purity DCPD70 to 85 wt. %
yDCPD/PIP
Pygas GT-BTXBenzene
Gasoline ygasHydrotreating
GT BTX Select ® Toluene
Xylenes
High-purity Styrene 99.9 wt. %
R i Oil
GT-Styrene®
Resin Oil
NaphthaleneResin OilNaphthalene
C6+ fraction
Aromatic SolventsPGO/PFOPGO/PFO(Fuel Stream)
Naphtha Cracker By-products C5sNaphtha Cracker By-products – C5s
• For naphtha cracking, by-product C5s are of 0.13-0.18 /ton of ethylene
• Diolefin C5 petrochemicals have much higher value than hydrotreating and recycle cracking
• Composition of C5s from a high severity naphtha cracker:
– 15% isoprene– 16% CPD, DCPD– 11% pips– 8% n-pentene– 11% isopentene11% isopentene– 4% cyclopentane, cyclopentene– 33% pentanes
2% t l th– 2% acetylenes, othersPage 10
Naphtha Cracker By-products – C5sMolecules and Applications
Primary Components of Interest
• Isoprene - 2 methyl-1,3 butadiene
• Piperylenes - cis trans/1 3 pentadienePiperylenes cis, trans/1,3 pentadiene
• CPD - cyclopentadiene
• DCPD - dicyclopentadiene
Other Components
• Isopentane Gasoline blend stock• Isopentane- Gasoline blend-stock• C5 Mono-olefins - TAME, catalytic cracking, aromatization, resin feedstock• Paraffins - Solvents, refrigeration, cracker feed
Page 11
C5 SeparationC5 Separation
Isopentane
Isoprene Extraction
IPR ‐ polymer Grade
C5 P ffi &
C5 Feed
C5 Paraffins & Mono Olefins
C5 splitting / Dimerization
DCPD andPIPS
DCPD and PIPS DCPD (70 ‐ 99%)
Heavies (Oligomers(Oligomers & Polymers)
Page 12
C5s to HCRBenefits of GTC’s Advanced C5 Process
• Lower energy and capital cost for C5 separation• Improved CPD/DCPD dimerization p• State-of-the-art separation• High value intermediates created for HCR
• Integrated C5 recovery/HCR product synergies• Improved feedstocks enhance performance of the HCRs• Improved system economics via pipeline return of non-reactives• Option for product off take of PIP’s and DCPD, with optional production
of isoprene if desired• Reduced energy and capital by matching PIP/DCPD spec to HCR plant• Reduced energy and capital by matching PIP/DCPD spec to HCR plant
needs
Naphtha Cracker By-products BTXNaphtha Cracker By-products – BTX
Liquid-Liquid Extraction Extractive DistillationH2O
Raffinate
Solvent
Raffinate
AromaticsE t t
AromaticsExtract
EDC SRC
Extract
Solvent
Feed EDC SRC
Feed
Naphtha Cracker By-products - StyreneNaphtha Cracker By-products - Styrene
Heartcut distillation followed by ED
C5C6
Light Cut
Pygas
C6C7
C C8 Cut GT St ® 99 9 wt %ygC8
C9
C8 Cut GT-Styrene® 99.9 wt.%Styrene
C9C10
Heavy CutHeavy Cut
Naphtha Cracker Styrene from Pygas -Economics
Parameters GT-Styrene®Capital Cost $30 MMCapital Cost $30 MMNet Feedstock Cost, $/ton $800 Processing Cost $/ton $250Processing Cost, $/ton $250 Total Production Cost, $/ton $1050 Sales Price, $/ton $1550, $ $Net Margin $12.50 MMPre-tax Contribution Margin 42%
• Basis: 25,000 MT/yr Styrene
Pygas Byproducts – C9 – C12 Naphthalene & Aromatic Solvents
• C9s - Hydrocarbon resin feedstock
• C10 – Naphthalene and derivatives (additive for concrete modifiers)
• C11 & C12 - Heavy aromatic solvents
Naphtha Cracker Pyrolysis Gas Oil (PGO)Co-products - Naphtha & Solvents
LightsLightsRemovalColumn
Purification System
C9 to HCR FeedWater
PGO Feed
Finishing Section Naphthalene
NaphthaleneFractionator Solvent Flasher
Solvent
PFO or Feed
Naphtha Cracker By-products Value Summary – 1000 KTA ethylene
Summary of Upgrade Options
C5 ‐ C12 Product AreaCapitalMM$
~ Payback( )MM$ (years)
C5Piperylene/DCPD ‐ GT‐C5 for HCRGT‐Isoprene™
2535
3
C6 Benzene (GT‐BTX®) 30 2
C7 Toluene (GT‐BTX®)GT T lAlk™
10 2GT‐TolAlk™
C8 Styrene (GT‐Styrene®) 30 2
C9 Resin Oil Solvents 10 1C9 Resin Oil, Solvents 10 1
C10 Naphthalene, Solvents 15 2
C11 C12 Aromatic Solvents 5 1C11 ‐ C12 Aromatic Solvents 5 1
GTC Technology is the only global licensor which offers all required technologies, and can assist in product placement.required technologies, and can assist in product placement.