Zeolite 3A and its application for ethanol dehydration

Dr. Van Dinh Son Tho Faculty of Chemical Technology HUT Prof. Le Hoai Nam Institute of Chemistry VAST Eng. Le Quang Vinh Institute of Chemistry VAST

Email: thovds-petrochem@mail.hut.edu.vn Tel : 097.360.4372

March 2009

CONTENTS :

1. Introduction for biofuel study in HUT

2. Synthesis of zeolite materials 3. Ethanol purification experiments 4. Pilot construction 5. Conclusion

Subject study at HUT

Subject
Synthesis bio-fuel Charaterization

Process
-Thermo-chemical technology - Fermentation technology -Liquid fuel, bio-gas - Bio-diesel and bio-ethanol

participants
FCT, IBFT, IHERE PCM

Purification
Physical properties testing Engine test

-PSA technology -Solvent extraction

ASTM standard for evaluation of the bio-fuel Engine test for bio-ethanol and bio-fuel Industries test

FCT, IBFT, IHERE

PCM IC.lab IHERE IE

Waste manegement

: Faculty of Chemical Technology IBFT : Institute of Biological-Fermentation IHERE : Institute of Heat Enginnering
FCT

PCM : Laboratory of Petrochemical Catalysis IC.lab : Internal Combustion laboratory IE : Institute of Enviroment

Technology for convert biomass into liquid fuel

1.

Thermal method
Wood, Baggase, Straw

Hydrocarbon gas Liquid fuel Bio-gas, Bio-gasoline, Bio-diesel

2.

Catalytic cracking
The sludge vegetable oil, used oil

3.

Tranestersification
Inedible oil, used oil

Bio-diesel

4.

Ethanol fermentation
Cassave, Sugar cane, corn

Ethanol

The demand and the capacity of Vietnam refinery production Demand (millions tons)
Product

Capacity of production
2020
Product

2005

2010

2015

Refinery No1 2,000

Refinery No2 2,100

Refinery No3 2,100

Gaoline

2,829

4,156

5,090

6,024

Gaoline

Diesel

5,800

8,740

11,140

13,024

Diesel

3,400

2,180

2,180

Cooking fuel JA1

440

420

392

360

Cooking fuel
JA1

200

200

419

615

844

1023

280

200

200

FO

2,878

3,665

4,350

5809

FO

120

270

270

The comparison of the demand and the produce of

GASOLINE products

Million tons

7000 6000 5000 4000 3000 2000 1000 0 2005 Demand 2010 Produce 2015 2020

2010

2015 4.156 1%

2020 5.090 3%

2025 6.024 5%

Gasoline consumption (Million ton)

The 117/CP Ethanol (Thousand ton)

2.829 0.4%

11.32

41.56

152.7

301.2

Dehydration of ethanol technology

1.
2.

Extractive distillation
Adsorption of water

3.
4. 5.

Azeotropic distillation
Molecular sieve technology Pervaporation

Ethanol research

Cassava

Ethanol

Distillation
96%

Adsorption

Fuel

99.5%

Synthesis of adsorption materials Characterization of adsorption materials Adsorption experiment Pilot construction Fuel test

Structure of zeolite

_ O
_ 2 2 _

O
2 _ 2 _

o Al
3+ 2

O
_

o Si4+ O
2

O
_

Fundamental Unit Tetrahedron of SiO4 or (AlO4)Secondary Building Unit (SBU)

The arrangement of SBU unit

4

S4R S6R

Soda l i t Sodalite

L n g tr 6 c n h

Linkage via D4R

Z eol i t k i u X (Y)

Zeolite Y

Zeolite A Z eol i t k i u A

H c l n

Large cavity

Selective adsorption
cages
Ethanol : 4.4Ao Water : 2.75Ao

cages

3.95Ao

cages Three dimensional framework of zeolite A

K+ exchange

zeolite 3A

Pore system of zeolite A

zeolite A
Na+ exchange

zeolite 4A

Synthesis of zeolite 3A
Si (husk) NaAlO2 Aluminum source Na2SiO3

Gel aging Crystalline Wash Dry & Calcine Cation exchange Zeolite 3A, 4A or 5A

Silica source

Characterization of zeolite 3A

791
751 667 404

D4R, D6R

467 553 1200 1100 1000 900 800 700 600 500

FTIR
NMR Al ZEOA1
4.50E+008 4.00E+008 3.50E+008 3.00E+008 2.50E+008

2-7

20-30

55-60ppm

Count

2.00E+008 1.50E+008 1.00E+008 5.00E+007 0.00E+000 -5.00E+007 -200

-100

100

200

Chemical shift (ppm)

NMR

XRD

3A zeolite sample

Adsorption experiments

Adsorption
12
350 100

4
300 250

Concentration of water (%) Cumulative volume of water

10

C(%)V(ml)H2O

V(ml)C2H5OH

C(%)C2H5OH

V(ml)H2O

200 98 150 100 50

6 2 4

2
96

0 0 0 20 40 60 80 100 120 140

Concentration of C2H5OH (%) Cumulative volume of C2H5OH

0 20 40 60 80 100 120 140 160 180

0 200

time(mins)

time(mins)

Relation of ethanol concentration and accumalate volume of ethanol versus with adsoprtion time

Relation of water concentration and accumalate volume of water versus with adsoprtion time

Adsorption experiments
v=0.539(m/s) v=0.522(m/s) v=0.237( m/s) v=0.24126(m/s) v=0.2585(m/s) ) v=0.18764 (m/s) v=0.1712(m/s)

100.0 99.5 99.0 98.5

C(%)C2H5OH

98.0 97.5 97.0 96.5 96.0 95.5 0 20 40 60 80 100 120 140 160 180 200

Adsorption time (Mins)

Calculation for adsorption process

Water adsorption of materials for full adsorption process (%- gH20/gZeolit) Water adsorption of materials for first adsorption process (%- gH20/gZeolit)

STT

Vapor velocity (m/s)

Vetanol 99,82% (ml)

0.171

98.6

11.46

4.71

4
3 1

0.246
0.522 0.539

96.2
42.8 55.3

10.83
10.35 12.63

4.59
2.04 2.64

40

De-sorption
Vapor velocity (m/s) Vetanol 99,8% (ml)

30

(% desorption)

20

10

0 200 250 300 350 400 450

Selectivity %

Temperature (oC)

Temperature desorption

0.171 0.246

98.6 96.2 42.8 55.3

35.5 40.5 39.4 36.4

40

0.522 0.539

% desoprtion

30

20

10

0 40 60 80 100 120 140 160 180 200 220

Temperature (oC)

Pressure desorption

Steps for the design of adsorption process

De-sorption process Adsorption of zone 1 Temperature or Pressure desoprtion Cp of zeolite Cp of water Cp of ethanol Cp of adsorption colum Amount of absorbed water and ethanol Adsorption column

Evaporation rate

Physical properties of zeolite 3 A

Cp of water Cp of ethanol Cp of evaporation still

Heat for evaporation Adsorption volume

Loss heat

Heat for de-sorption

Energy demand for the evaporation

Energy for de-sorption

Design of the pilot adsorption system

Equipments for the adsorption system

Unit Ethanol Tank Adsorption column Liquid vapor separator Evaporator Calorie 25-150oC Calorie 400oC Condenser for anhydrous ethanol Condenser for de-sorption Ethanol pump Quantity 1 2 1 1 1 1 1 1 1

Vacuum pump (Blue-white)

Heater Temperature controller Vapor controller Gas flow controller Accessories

1
1 8 1 3

Adsorption column

Ethanol pump Evaporator

Ethanol fuel tank Liquid Vapor seperator

Adsorption colunm 1, 2

Calorie 1, 2

Evaporator

Condenser 1, 2

Ethanol tank

Conclusion
1.
2.

Successful synthesis zeolite 3A

Fix bed adsorption experiments for evaluation adsorption ability of zeolite and examination parameters of the adsorption and de-sorption processes. Design and construct the pilot system for ethanol concentration.

3.

Further study
Evaluation the technology of adsorption process by PSA by pilot system Examination the energy consumption of the process. Ethanol fuel characterization. Engine test.

Lab of Crude oil and petroleum products

Fractionation distillation of crude oil (i-Fisher)

Bomb calorimeter (Parr)

Light fraction distillation (Koehler)

Kinematic viscosity (Koehler)

Oxidation stability (Koehler)

Autoflash (Gallenkamp) and Copper strip corrsosion meter (Koehler)

Lab of Catalysis Materials

XRD (Brucker)

Physi and chemisorption systems (Micromeritics)

TGA-DTA-DSC (Netzsch)

Particle size analyzer (Horiba)

FTIR-Raman (Thermo Nicolet)

AAS (Analytik Jena)

Lab of Petrochemical Processes

Atmospheric Microactivity catalytic test system (Zeton)

Hydrotreating system (Vinci)

GC online Microactivity test systems (Home made)

Hydrocarbon analyzer (Thermo Finnigan)

GC/MS (Thermo Finnigan)

Simulation system (Hysys)

Motorcycle chassis dynamometer Roller diameter : 20 (508 mm) Motorcycle weight: 80 - 350 kg Max. Speed : 160 km/h