1. CRACKED GAS APPLICATION
Zeochem Molecular Sieve
Z3-02

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

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

4. 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 °C
Pressure bar
Regen.Temp. 230°C
Regen. Gas Dry, low Olefin content

5. 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

6. 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)

7. 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

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

9. 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)

10. Cracked Gas Dehydration Kinetic Comparison, Hiden

11. 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

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

13. 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

14. Cracked Gas Dehydration Zeochem / Competition - Field Decay Curves

15. 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

16. 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)

17. Cracked Gas Dehydration Pressure Drop Field Data

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

19. 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 g/L
Zeochem Z3-02
2.5-5 mm Beads
Competitive Type 3A
1/8" Extrudates

20. 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

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

22. Cracked Gas Dehydration Operating Costs
Basis Two Beds Initial 72 hour adsorption time
Flow Rate '000 Nm3/h
Temperature °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)

23. Cracked Gas Dehydration Comparison Z3-02 Beads / Extrudates

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

25. 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

26. 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

27. 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

28. 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