CRACKED GAS APPLICATIONCRACKED GAS APPLICATION

Zeochem Molecular Sieve Zeochem Molecular Sieve

Z3-02 Z3-02

CRACKED GAS APPLICATIONCRACKED GAS APPLICATIONIntroduction - Olefin ProductionIntroduction - Olefin Production

Natural Gas

CH4 , C2H6 , C3H8

Crude Oil

Naphta , Gasoil, LPG

CRACKING PROCESSCRACKING PROCESS

FEEDSTOCKSFEEDSTOCKS

CRACKED GAS APPLICATIONCRACKED GAS APPLICATIONOlefin Production - StepsOlefin Production - Steps

Acid Gas Acid Gas RemovalRemoval

Pressurisation Pressurisation

CrackingCracking

Molecular Sieve Molecular Sieve DehydrationDehydration

Olefin SeparationOlefin Separation

CRACKED GAS APPLICATIONCRACKED GAS APPLICATIONOlefin Dehydration with Molecular Olefin Dehydration with Molecular SievesSieves 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 APPLICATIONCRACKED GAS APPLICATIONOlefin Dehydration with Molecular Olefin Dehydration with Molecular SievesSieves Process Design

– according to cracker process– long cycle times Reduced Regen.

Cycles– high water adsorption capacity– smooth regeneration– low P

Product Gas Quality– < 1ppm moisture or DP < -100°C

Cracked Gas DehydrationCracked Gas DehydrationZeolite as Molecular Sieve 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 DehydrationCracked Gas DehydrationMolecular Sieving Effect 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 DehydrationCracked Gas DehydrationZZeolite Manufacturing Processeolite Manufacturing Process

Al(OH)3 NaOH

NaHSiO3

H2O, KCl

3A-Pulver3A-Pulver

Bead Formation

Binding Clay

Activation Z3-02Z3-02

* Quality Control* Quality Control**

* *

**

** **

**

Cracked Gas DehydrationCracked Gas DehydrationQuality Control of Molecular Sieve Quality Control of Molecular Sieve Z3-02Z3-02

Characterisation– residual water content– CO2 adsorption

capacity– T 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 DehydrationCracked Gas DehydrationKinetic Comparison, HidenKinetic Comparison, Hiden

02468

101214161820

0 50 100 150 200 250[min]

[%w

w]

Competitive Type 3A, 1/8" extr.:120 min.: 13.4 %

ZEOCHEM Z3-02, 2-3 mm beads120 min: 14.2 %

Cracked Gas DehydrationCracked Gas DehydrationKey Properties of Molecular Sieve Key Properties of Molecular Sieve Z3-02Z3-02

High water adsorption capacity Low pressure drop (P) Good thermal and hydrothermal stability Low coke formation High freeze - thaw resistance High density

Cracked Gas DehydrationCracked Gas DehydrationDesign and Field Decay Curves for Design and Field Decay Curves for Z3-02Z3-02

5

10

15

20

0 50 100 150 200 250 300 350 400Number Of Cycles

Cap

acity

W

t %

Field

Design

Cracked Gas DehydrationCracked Gas DehydrationKey Properties of Molecular Sieve Key Properties of Molecular Sieve Z3-02Z3-02

High Water Adsorption Capacity High Water Adsorption Capacity

and Good Hydrothermal Stabilityand Good Hydrothermal Stability

• lower heat energy requirement• longer cycle times resp. less cycles • slower capacity decay• long life time characteristics

Cracked Gas DehydrationCracked Gas DehydrationZeochem / Competition Zeochem / Competition - - Field Decay Field Decay CurvesCurves

Ethylen Plant - Petromont - Varennes, Quebec

40

45

50

55

60

65

70

75

0 20 40 60 80 100 120

Cycle Number

Cycl

e Ti

me

(h)

Cracked Gas Dryer Molecular Sieve Continuing Performance

Zeochem Z3-02 in bed A installed July 7, 1995

Zeochem Z3-02 in Bed B installed June 23, 1994

Competitive Type 3A in Bed A Discharged after 23.5 months

Cracked Gas DehydrationCracked Gas DehydrationKey Properties of Molecular Sieve Key Properties of Molecular Sieve Z3-02Z3-02

Low Catalytic Binder Activity andControlled Formulation in Production

Low coke formation• high lifetime• high adsorption performance• Unsaturates and by-products remain outside pores

Cracked Gas DehydrationCracked Gas Dehydration Pressure Drop calculationPressure Drop calculation

Modification of Ergun EquationModification of Ergun Equation

PP//LL = A = AUUV V + B+ BRRVV22

psipsi viscosity (cP) viscosity (cP) gas gas density (lb/ftdensity (lb/ft33))

Bed height (ft) Bed height (ft) fluid fluid velocity (ft/minvelocity (ft/min)Particle size A B

2.5-5 mm or 4x8 US mesh 0.056 8.89 10-5

2-3 mm or 9x16 US mesh 0.156 1.36 10-4

1-2 mm or 8x12 US mesh 0.352 2.07 10-4

1/ 8“ pellet (extrudate) 0.0732 1.24 10-4

1/ 16“ pellet (extrudate) 0.238 2.01 10-4

Cracked Gas DehydrationCracked Gas DehydrationPressure Drop Field DataPressure Drop Field Data

Ethylene Plant North America

100.0

150.0

200.0

250.0

300.0

350.0

6.11

11.1

119

.11

22.1

125

.11

28.1

11.

124.

127.

12

10.1

213

.12

16.1

221

.12

25.1

231

.12 3.

16.

1

Date

Pressure drop (mbar)

270 mbar

210 mbar

Competitive Pellets

Zeochem Beads Z3-02

Pressure Drop Comparison - 3 Beds Parallel

Cracked Gas DehydrationCracked Gas DehydrationPressure Drop ComparisonPressure Drop Comparison

Lower P (Beads instead of extrudates)

• lower compression costs (- 20...25%)• allows higher flow rates

Cracked Gas DehydrationCracked Gas DehydrationPhysical Stability ComparisonPhysical Stability Comparison

max. 3.0max. 3.0

max. 3.0max. 3.0------

>90>90

Freeze-Thaw Freeze-Thaw TestTest

ChipsChips

Broken BeadsBroken Beads

max. 50max. 50524524Dust Index Dust Index (Heubach) (Heubach) ppmppm

750 750 +/-+/- 20 20660660Bulk DensityBulk Density

ISO 787 ISO 787 g/Lg/L

Zeochem Z3-02Zeochem Z3-02

2.5-5 mm Beads2.5-5 mm BeadsCompetitive Type Competitive Type 3A3A

1/8" Extrudates1/8" Extrudates

Cracked Gas DehydrationCracked Gas DehydrationKey Properties of Molecular Sieve Key Properties of Molecular Sieve Z3-02Z3-02

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 DehydrationCracked Gas Dehydration COST COMPARISON Z3-02 BEADS VERSUS COST COMPARISON Z3-02 BEADS VERSUS EXTRUDATESEXTRUDATES

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 DehydrationCracked Gas DehydrationOperating CostsOperating Costs

BasisBasis 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 / BedMolecular Sieve / Bed 52 cubic meters52 cubic metersAdsorption timeAdsorption time 72 hours initial72 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 DehydrationCracked Gas DehydrationComparison Z3-02 Beads / ExtrudatesComparison Z3-02 Beads / Extrudates

Adsorbent Type / Parameters

Zeochem Z3-02 Beads Split Bed

Typical 3A 1/8“ Extrudate

Pressure Drop mbar 240 310 Regeneration heat KWh 2’400 2’400 COST SUMMARY US$ per year

Press. Drop cost over 4 year 348’480 450’120 Heating cost Year 1 38’970 43’300 Year 2 47’790 53’100 Year 3 62’010 68’900 Year 4 87’390 97’100 Total Costs US $ 584’640 712’520

Savings US $ 127’880

POLYMER GRADEPOLYMER GRADEOLEFIN TREATMENTOLEFIN TREATMENT

Molecular Sieve Z3-02 and Z10-03Molecular Sieve Z3-02 and Z10-03

POLYMER GRADE OLEFINSPOLYMER GRADE OLEFINSPre- PurificationPre- 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 OLEFINSPOLYMER GRADE OLEFINS ADVANTAGES OF ZEOCHEM Z10-03ADVANTAGES 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 OLEFINSPOLYMER GRADE OLEFINSPre-PurificationPre-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 Cracked Gas DehydrationDehydrationSummarySummary 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