CRACKED GAS APPLICATION Zeochem Molecular Sieve Z3-02

CRACKED GAS APPLICATION Introduction - Olefin Production Crude Oil Naphta , Gasoil, LPG Natural Gas CH4 , C2H6 , C3H8 FEEDSTOCKS CRACKING PROCESS

CRACKED GAS APPLICATION Olefin Production - Steps Cracking Acid Gas Removal Pressurisation Molecular Sieve Dehydration Olefin Separation

CRACKED GAS APPLICATION Olefin Dehydration with Molecular Sieves Adsorption Process: 3A - Type molecular sieve Temperature Swing Adsorption (TSA) Reactive components in stream ( , C C ) Conditions: Temp. 5 - 15°C Pressure 20 - 30 bar Regen.Temp. 230°C Regen. Gas Dry, low Olefin content

CRACKED GAS APPLICATION Olefin Dehydration with Molecular Sieves Process Design according to cracker process long cycle times Reduced Regen. Cycles high water adsorption capacity smooth regeneration low DP Product Gas Quality < 1ppm moisture or DP < -100°C

Cracked Gas Dehydration Zeolite as Molecular Sieve Alumino-silicate Na2O.Al2O3.SiO2.xH2O microcristalline structure A-Types : 3A (K- Form): 0.3 nm pores 4A ( Na-Form): 0.4 nm pores 5A ( Ca-Form): 0.5 nm pores 13X- Type: 0.8 nm pores (Na-form)

Cracked Gas Dehydration Molecular Sieving Effect Sieving Effect based on: molecule size or diameter molecules with D<0.3nm can be adsorbed in a 3A Sieve : i.e. H20, NH3, H2, He molecules with D < 0. 4 nm can be adsorbed in a 4A Sieve: i.e. H2O, CO2, H2S, C2H6, C2H4 polarity of the molecules Increased affinity with increasing polarity H20 > RSH > H2S > C2H4 > CO2

Cracked Gas Dehydration Zeolite Manufacturing Process NaHSiO3 * Quality Control * Al(OH)3 NaOH H2O, KCl Binding Clay * * * * Bead Formation Activation Z3-02 * 3A-Pulver

Cracked Gas Dehydration Quality Control of Molecular Sieve Z3-02 Characterisation residual water content CO2 adsorption capacity DT MeOH crystallinity ( X-ray diffraction) SEM bulk density: 750 elemental analysis under- & oversize Stability attrition freeze thaw test boiling water test crush strength Process parameter kinetic measurement (MTZ, Hiden)

Cracked Gas Dehydration Kinetic Comparison, Hiden

Cracked Gas Dehydration Key Properties of Molecular Sieve Z3-02 High water adsorption capacity Low pressure drop (DP) Good thermal and hydrothermal stability Low coke formation High freeze - thaw resistance High density

Cracked Gas Dehydration Design and Field Decay Curves for Z3-02

Cracked Gas Dehydration Key Properties of Molecular Sieve Z3-02 High Water Adsorption Capacity and Good Hydrothermal Stability lower heat energy requirement longer cycle times resp. less cycles slower capacity decay long life time characteristics

Cracked Gas Dehydration Zeochem / Competition - Field Decay Curves

Cracked Gas Dehydration Key Properties of Molecular Sieve Z3-02 Low Catalytic Binder Activity and Controlled Formulation in Production Low coke formation high lifetime high adsorption performance Unsaturates and by-products remain outside pores

Cracked Gas Dehydration Pressure Drop calculation Modification of Ergun Equation DP/L = AUV + BRV2 psi viscosity (cP) gas density (lb/ft3) Bed height (ft) fluid velocity (ft/min)

Cracked Gas Dehydration Pressure Drop Field Data

Cracked Gas Dehydration Pressure Drop Comparison Lower DP (Beads instead of extrudates) lower compression costs (- 20...25%) allows higher flow rates

Cracked Gas Dehydration Physical Stability Comparison max. 3.0 --- >90 Freeze-Thaw Test Chips Broken Beads max. 50 524 Dust Index (Heubach) ppm 750 +/- 20 660 Bulk Density ISO 787 g/L Zeochem Z3-02 2.5-5 mm Beads Competitive Type 3A 1/8" Extrudates

Cracked Gas Dehydration Key Properties of Molecular Sieve Z3-02 Physical Stability through FREEZE-THAW Resistance Pressure reduction during regeneration causes large temperature reduction Ice formation causes bead expansion Freeze-thaw test simulates bead expansion forces

Cracked Gas Dehydration COST COMPARISON Z3-02 BEADS VERSUS EXTRUDATES BASIS: Typical Heat Cost 6.83 US$ per MWh, Typical Compression Cost 2.42 US$ / mbar / 1000 Nm3/hr per year. Same volume per column

Cracked Gas Dehydration Operating Costs Basis Two Beds Initial 72 hour adsorption time Flow Rate 150'000 Nm3/h Temperature 12°C Pressure 20 bara Molecular Weight 23 Regeneration Time 12 hours heat at 230°C Service Lifetime 4 years Molecular Sieve / Bed 52 cubic meters Adsorption time 72 hours initial 60 hours at the end of year 1 (66 cycles) 48 hours at the end of year 2 (81 cycles) 36 hours at the end of year 3 (105 cycles) 24 hours at the end of year 4 (146 cycles)

Cracked Gas Dehydration Comparison Z3-02 Beads / Extrudates

POLYMER GRADE OLEFIN TREATMENT Molecular Sieve Z3-02 and Z10-03

POLYMER GRADE OLEFINS Pre- Purification Polymerisation catalysts are very sensitive to impurities. Zeochem recommends either Z10-03: Dehydration plus oxygenates & sulphur compounds removal, or Z3-02: in combination with Selexsorb* COS to remove oxygenates, sulphur compounds, COS * trade name of Alcoa Inc

POLYMER GRADE OLEFINS ADVANTAGES OF ZEOCHEM Z10-03 Selective for removal of moisture oxygenates, carbon dioxide, sulphur compounds (H2S, mercaptans) Outlet concentrations < 0.1 ppm Good flow distribution Long Life Excellent mechanical properties

POLYMER GRADE OLEFINS Pre-Purification Alternative technology uses Z3-02 for dehydration in a dual bed system with Selexsorb* COS Selexsorb* COS removes oxygenates and sulphur compounds including carbonyl sulphide prior to dehydration * trade name of Alcoa Inc

Cracked Gas Dehydration Summary High Quality Products Zeochem Z3-02 and Z10-02 Technical Service including: Design Engineering Start up with Loading Instruction Process Assistance with Follow –up Highly qualified Laboratory for investigations set the foundations for reliability and top Performance