GTC Technology Day. 16 April Hotel Le Meridien New Delhi. Pyrolysis Gasoline Value Upgrades Styrene

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1 16 April Hotel Le Meridien New Delhi Pyrolysis Gasoline Value Upgrades Styrene

2 Naphtha Cracker Byproducts Pygas GTC-offered Overall Processing Scheme Raw Pyrolysis Gasoline C 5 Fraction Pygas Hydrotreating Crude Isoprene Extraction GT-BTX Select GT-Styrene High-Purity Isoprene High-Purity DCPD/PIPs CyC6 Isopentane C 5 to recycle cracking High-purity Isoprene Piperylenes High-purity DCPD 70 to 85 wt. % Benzene Cyclohexane Toluene Xylenes High-purity Styrene 99.8 wt. % C 6 + Fraction PGO/PFO (Fuel Stream) Resin Oil Naphthalenes Resin Oil Naphthalenes Aromatic Solvents 2

3 Economical to Produce Economical Ethylene Capacity for Recovering By-products, Secondary Deriv. Naphthalene, Secondary Deriv. Isoprene, DCPD, Pips Styrene Extraction, C 9 Resins Butadiene, Benzene, Toluene, Xylenes Ethylene, Propylene, Primary Derivations Ethylene rate, KTA (Liquids feed) 3

4 Pygas Upgrade 4

5 C5 Utilization Options Target for Gasoline Alkylation ic4 + C5 olefin Alkylate Etherification ic5 - + MeOH TAME Target for Petrochemicals PIPs & DCPD Recovery Dimerization, Fractionation Isoprene Recovery Extraction, Reaction, Superfractionation Aromatization C5/C5 - Aromatics Olefin Cracking C5 - C3 - Metathesis C2 - + C5 - C3-5

6 Pygas C5 Utilization GTC GT-C5 Lights Mono Olefins/ Paraffins High Purity Isoprene Raw C5 Lights Removal Section Extraction Section Finishing Section Dimerization Section C5 Splitter Section C6 Stream PIPS and DCPD Finishing Section PIPS %DCPD 85 %DCPD 6

7 Pygas Upgrade 7

8 GT-BTX : World-Class Extraction Technology for BTX Purification Hydrocarbon Feed Lean Solvent Extractive Distillation Column (EDC) Raffinate Solvent Recovery Column (SRC) Aromatics to Downstream Fractionation Aromatics Rich Solvent TECHTIV 100 (500) Solvent 8

9 GT-BTX Compared to Other ED Systems TECHTIV 9

10 Pygas Upgrade 10

11 Fundamentals of Styrene Production Typical components in a pygas stream include: Paraffins Olefins Diolefins Aromatics Aromatic olefins Close-boiling components 11

12 Styrene And Close-boiling Pygas Components C CH 2 C CH 3 CH 3 Styrene NBP 145 o C Ethylbenzene NBP 136 o C Orthoxylene NBP 144 o C CH 3 C CH CH 3 C CH 3 Phenyl Acetylene NBP 142 o C Dicyclopentadiene NBP 152 o C Cumene NBP 152 o C 12

13 Separation between Styrene and Close-boiling Components Solvent-based system to extract and purify styrene Extractive distillation alters boiling points of components Component NBP ( o C) Relative Volatility to Styrene Relative Volatility to Styrene (Enhanced) Styrene Ethylbenzene Ortho-xylene DCPD

14 Extractive Distillation Solvent Selection Large increase in relative volatility Must be thermally and chemically stable Must be conveniently separated from styrene 14

15 Extractive Distillation Solvent Selection Large increase in relative volatility Must be thermally and chemically stable Must be conveniently separated from styrene Through intensive research & process development, GTC has designed an optimum solvent blend, Techtiv

16 Separation Strategy for Styrene Recovery Heart cut distillation followed by ED (Extractive Distillation) C 5 C 6 C 7 Light Cut Pygas C 8 C 8 Cut GT-Styrene 99.8 wt.% Styrene C 9 C 10 Heavy Cut 16

17 Process Flow Scheme for Styrene Recovery Crude C 4 Catalyst life extended H2 consumption reduced to half Raw C 5 H 2 H 2 H 2 S C 6 C 8 Raffinate DeC 4 1 st Stage 2 nd Stage GT-BTX Select Benzene DeC 5 Toluene Xylenes Pyrolysis Condensates GT-Styrene Styrene DeC 7 DeC 7 C 9 + High value SM product Price increase by reducing EB and upgrade from lower-value solventgrade mixed xylenes 17

18 GT-Styrene Recovery of styrene from the raw pyrolysis gasoline derived from the steam cracking of naphtha, gas oils, and natural gas liquids (NGL) H 2 Finishing Treatment C 8 Aromatics 99.8 wt% Styrene Product Pygas C 8 Cut PA Hydrogenation Lean Solvent Heavies Feed Treatment Extractive Distillation Solvent Recovery Styrene Finishing 18

19 Competitive Advantages Produces polymer-grade styrene at 99.8% purity, meeting all quality standards of ASTM D Great value upgrade from pygas value to SM value Allows the recovery of mixed lower-eb mixed xylenes for paraxylene production Debottlenecks pygas hydrotreater and extends cycle length Reduces hydrogen consumed in pygas hydrotreating very significantly Reduces energy consumption for pygas hydrotreating and aromatics extraction units Advanced distillation techniques and equipment give highest efficiency and performance 19

20 Competitive Advantages, continued Highest efficiency Techtiv-200 solvent. More effective than any other system tested from over 50 commercial solvents. Gives the most optimized performance and economical operating costs Highest selectivity PA reduction using Clariant catalyst Novel oxygenate removal system Simple and effective color treatment system. No nitric-acid washing or nitrogen contaminants in the product 20

21 Process Performance Typical feed: Component wt% C 7-2 Ethyl benzene 8 Mixed xylene 42 Styrene 38 C 9+ aromatics 0.5 Non-aromatics 10 Styrene recovery 95% Styrene purity 99.8 wt% 21

22 Typical ASTM Specification for International Trade Component Specification Styrene, wt% 99.8 min. Phenyl acetylene, ppm 50 max EB+Xylenes, wt% 0.1 max Aldehydes, ppm 200 max Peroxides, ppm 100 max Color, APHA 10 Polymer, ppm 10 max Inhibitor, ppm

23 Economics For Styrene Recovery Typical USGC grassroots capital cost (ISBL) Styrene value in pygas (solvent-grade mixed xylenes value processing cost to extract mixed xylenes) Styrene product sales value Net processing cost Net profit (GT-Styrene unit) Mix-xylenes value upgrade Net profit (mix-xylene value upgrade; considering 25,000 tpa mixed xylenes from pygas) H2 saving Hydrotreating catalyst life extension Pygas hydrotreating unit debottleneck Total net profit Simple annual ROI $30 million $653/ton (FOB Korea) $1375/ton (FOB Korea) $140/ton $19.2 million/yr $50/ton of mix-xylenes $1.6 million/yr User to consider its value User to consider its value User to consider its value 20.9 million/yr 69.5% (1.4 year), or 64.0% (1.6 year) if not including mixed xylenes upgrade Basis: a) Based on 33,000 tpa styrene b) Prices at (IHS Report) 23

24 Summary GT-Styrene provides excellent value for naphtha crackers with >500,000 tpa ethylene capacity Styrene production from pygas as the raw material, having much larger gross margin than conventional styrene production from benzene + ethylene Commercial proven process, with styrene product used in various styrene downstream polymers Reduction of EB content in the mixed-xylenes Great pull-through benefits for pygas hydrotreating unit by removing styrene in the feed Energy saving in the all pygas units after GT-Styrene 24

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