ETHANOL DEHYDRATIONETHANOL DEHYDRATION

WITHWITH

ZEOCHEM MOLECULAR SIEVE ZEOCHEM MOLECULAR SIEVE

Z3-03Z3-03

ETHANOL DEHYDRATION ETHANOL DEHYDRATION THE DUTYTHE DUTY

Liquid phase technology - older technology. Gas phase technology - modern technology

- Use an adsorbent to get past the azeotrope. Molecular sieves best technology due to

– simplicity– low installation cost– environmentally friendly– low energy usage

LIQUID PHASE DEHYDRATIONLIQUID PHASE DEHYDRATION

Thermal Swing Technology

characterised by Low temperature adsorption Long cycle times - up to 8 hours High capacity - up to 20% Thermal Regeneration Slower velocity, longer MTZ

GAS PHASE DEHYDRATIONGAS PHASE DEHYDRATION

Pressure Swing Technology characterised by Lower capacity typically 1-4% Short cycle times (2 -30 minutes) High temperature / pressure adsorption Low pressure regeneration (vacuum) Need for high strength product

ETHANOL DEHYDRATIONETHANOL DEHYDRATIONwith Molecular Sieveswith Molecular Sieves

Adsorption Process:– 3A - Type molecular sieve– Pressure Swing Adsorption (PSA)

Conditions:– Temp. 100 - 150°C– Pressure Ads. 1.5 – 2.0 bar

Des. ca. 100 -200 mbar

– Regen. gas dry Ethanol– Cycle Times 10 – 30 min.

ETHANOL DEHYDRATIONETHANOL DEHYDRATIONwith Molecular Sieveswith Molecular Sieves

Alumino-silicate Na2O.Al2O3.SiO2.xH2O

microcrystalline 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)

ETHANOL DEHYDRATIONETHANOL DEHYDRATIONwith Molecular Sieveswith Molecular Sieves

Sieving Effect based on: molecule size or diameter

– molecules with D<0.3nm can be adsorded

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, C2H4

polarity of the molecules– affinity encreasing with polarity– H20 > RSH > H2S > C2H4 > CO2

Ethanol Grade Molecular SieveEthanol Grade Molecular SieveZZeolite Manufacturing Processeolite Manufacturing Process

Al(OH)3 N aOH

NaHSiO3

H2O, KCl

3A-Pulver3A-Pulver

Bead Formation

Binding Clay

Activation Z3-03Z3-03

* Quality Control* Quality Control**

* *

**

** **

**

Ethanol DehydrationEthanol DehydrationQuality Control of Molecular Sieve Z3-03Quality Control of Molecular Sieve Z3-03

Characterisation– residual water content

– CO2 adsorption capacity

– crystallinity ( X-ray diffraction)

– SEM– bulk density: 740– elemental analysis– under- & oversize

Stability– attrition– freeze thaw test– boiling water test– crush strength

Process parameter– kinetic measurement

(MTZ)

Ethanol DehydrationEthanol DehydrationKinetic ComparisonKinetic Comparison

02468

101214161820

0 50 100 150 200 250[min]

[%w

w]

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

ZEOCHEM Z3-03, 2-3 mm beads120 min: 14.2 %

Ethanol DehydrationEthanol DehydrationKey Properties of Molecular Sieve Z3-03Key Properties of Molecular Sieve Z3-03

High water adsorption capacity Low pressure drop (DP) Good thermal and hydrothermal stability Low by product formation (DEE, AcH, DEA) High density (740 g/l) High Crush Strength Low Attrition Good Kinetics

Ethanol DehydrationEthanol DehydrationKey Properties of Molecular sieve Key Properties of Molecular sieve Z3-03Z3-03

Exceptional Physical Properties High Crush Strength Low Attrition

Low Catalytic Binder Activity andControlled Formulation and Production

Exceptionally Low Formation of By products

Low Coke Formation High Lifetime High Adsorption Performance

Ethanol DehydrationEthanol DehydrationPhysical Stability ComparisonPhysical Stability Comparison

max. 3.0max. 3.0

max. 3.0max. 3.0

------

>90>90

Freeze-thaw testFreeze-thaw test

ChipsChips

Broken beadsBroken beads

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

max. 0.1max. 0.10.50.5Attrition (%) Attrition (%)

Zeochem Z3-03Zeochem Z3-03

2.5-5 mm Beads2.5-5 mm Beads

Competitive Type 3ACompetitive Type 3A

1/8" Extrudates1/8" Extrudates

ZEOCHEM Z3-03ZEOCHEM Z3-03Ethanol DehydrationEthanol Dehydration

SummarySummary

High Quality Product Zeochem Z3-03 High Reputation and Many Successful

References Worldwide

Zeochem Z3-03Zeochem Z3-03Reference Plants with Katzen DesignReference Plants with Katzen Design

Jamaica Ethanol, Kingston 30'000 lbs

Laica, Costa Rica 107'000 lbs

Planalcool, Brazil 117'000 lbs

44'000 lbs

Golden Triangle, Craig, Co 40'000 lbs

Dacota Ethanol, Sioux Falls, SD 160'000 lbs

JR Simplot, Caldwell, ID, USA 15'000 lbs

Akwawit, Lesno, Poland 58'200 lbs

OPERATIONAL PARAMETERSOPERATIONAL PARAMETERS

Ethanol molecule very polar - only slightly less polar than water

Need molecular sieve with controlled pore size to exclude ethanol

Need good kinetic performance Need good strength beads for PSA system