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.

GTC TechnologyGTC Technology

www.gtctech.com