Effect of Al2O3, SiO2 and TiO2 on molibdenum oxidesupported catalyst in ethanol oxidation into acetaldehyde

Husni Husin

Chemical Engineering DepartmentEngineering FacultySyiah Kuala UniversityDarussalam Banda AcehIndonesia

Introduction

IMPORT !

Acetaldehyde: intermediate productraw material: pentaeritrytol and acetic acid production

Conventional pocess: petrochemical via X < 72, Y < 95Catalyst : SilverVery Expensive metal

⎯⎯⎯ →⎯ °CAg 500,

Reaction :

CH≡CH + H2O CH2 = CHO H C2H4O P = 15 psi

CH3CH2OH + ½O2 CH3CHO + H2O

T = 300 – 575 oC , P = 1 atm

⎯⎯⎯⎯⎯⎯⎯ →⎯ −+ CSOHHg o1000700,, 422

⎯⎯⎯⎯⎯⎯⎯ →⎯ −+ CSOHHg o1000700,, 422

⎯⎯⎯ →⎯ °CAg 500,

high cost

Alternative Route

Reaction:C2H5OH+½ O2 →C2H4O+H2O

Ethanol Oxidation over MoO3 based Catalyst

-This research is objected to evaluate the Influnce of TiO2, Al2O3, SiO2 on MoO3 catalyst in ethanol oxidation into acetaldehyde

1. Viswanath (1982)Catalyst : Fe/Mo/OT = 200-320˚C

2. Mc Cabe dan Machiels (1983)- Catalyst: mangane, platinum, dan Copper

3. Filho dan Domingues (1992 )- Catalyst : Fe/Mo/O komersial - T: 180-243 0C P: atm

4. Zhang dkk (1995) :- Catalyst : MoO3 syntetis

5. Husin dkk,. (2002)- Catalyst Fe2O3.MoO3

ETHANOL

Literature Study

Catalyst and Condition ???

Catalyst Preparation

(NH4)6Mo724O2.4H2O Al2O3, TiO2, SiO2

Impregnation

Drying

Calsination

MoO3/Al2O3, TiO2, SiO2 Catalyst

Catalyst Preparation

Characterization

Catalyst Test

Reactor set up

feedinjectionthermocople

reactor

condenser

catalystbuble

soap

flowm

eter

Gas mixer

detector

Vent

Methanol

liquid Product

gas product

H2O absorberpreheater

nitro

gen

oxige

n

nitro

gencontroller

RESULT AND DICCUSSION

XRD data

Figure 3.a Diffractogram of MoO3/TiO2

x

x

t

xt

tx x tt x

0

1000

2000

3000

4000

10 20 30 40 50 60 702 Theta (degree)

Inte

nsity

(cps

)

25% MoO3/TiO2

t ttxxt

x

xtx

x

x

0

1000

2000

3000

4000

10 20 30 40 50 60 702 Theta (degree)

Inte

nsity

(cps

)

50% MoO3/TiO2

XRD data

Figure 3.b Diffractogram of MoO3/Al2O3

x

2 Theta (degree)

6000

5000

4000

3000

Intensity (cps)

2000

1000

0

50% MoO3/Al2O3x = MoO3o = Al2O3

10 20 30 40 50 60 70

x

x

xo

x

xxx

xx

xo

xo

xo

o

Intensity

2 Theta (degree)

2000

1000

0

3000

4000Intensity (cps)

5000

25% MoO3/Al2O3x = MoO3o = Al2O3

10 20 30 40 50 60 70

x

x

xx

xx

xo

xo x

oo

Intensity

6000

XRD data

Figure 3.c Diffractogram of MoO3/SiO2

10 20 30 40 50 60 70 10 20 30 40 50 60 70

6000

4000

2000

0

50% MoO3/SiO2x = MoO3s = SiO2

2 Theta (degree)

1000

5000

00

x

s x

xx

xxs

xs

s

xs

Intensity

6000

4000

2000

0

25% MoO3/SiO2x = MoO3s = SiO2

2 Theta (degree)

5000

00

1000

x

xs

s

xxx

xs

s

xs

x

Intensity

Catalytic Activity

Figure 4. Conversion, Selectivity, and yield for ethanol oxidation at different temperature over 25% MoO3/Al2O3, TiO2, and SiO2

0102030405060708090

100

125 150 175 200 225 250 275 300 325Temperature (oC)

Akt

ivita

s (X

, S, Y

) %

Konversi EtanolSelektivitas AsetaldehidaYield Asetaldehida

25 % Mo O3/Al2O3

0

20

40

60

80

100

125 150 175 200 225 250 275 300 325Temperature (oC)

Akt

ivita

s (X

, S, d

an Y

) %

Konversi EtanolSelektivitas AsetaldehidaYield Asetaldehida

25 % Mo O3/TiO2

0102030405060708090

100

125 150 175 200 225 250 275 300 325Temperature (oC)

Akt

ivita

s (X

, S, Y

) %

Konversi EtanolSelektivitas AsetaldehidaYield Asetaldehida

2 5% MoO3 /SiO2

Figure 4. Conversion, Selectivity, and yield for ethanol oxidation at different temperature over 50% MoO3/Al2O3, TiO2, and SiO2

Catalytic Activity

01 02 03 04 05 06 07 08 09 0

1 0 0

1 2 5 1 5 0 1 7 5 2 0 0 2 2 5 2 5 0 2 7 5 3 0 0 3 2 5

T em p erat ur (o C)

Akt

vita

s (X

, S, d

an Y

) %

K o n v ersi E t an o lSelek t iv it as A set aldeh idaY ield A set aldeh ida

1 0 0 % M o O 3

0102030405060708090

100

125 150 175 200 225 250 275 300 325T emperat ure (oC)

Akt

ivita

s (X

, S, Y

) %

Konversi Et anolSelekt iv it as Aset aldehidaYield Aset aldehida

5 0 % M o O3 / S iO2

0102030405060708090

100

125 15 0 175 200 225 250 275 3 00 325T em perat ure (oC)

Akt

ivita

s (X

, S, Y

) %

Konversi Et ano lSelek t iv it as Aset aldeh idaYield Aset aldeh ida

5 0 % M o O 3 / A l2 O 3

0102030405060708090

100

125 150 175 2 00 225 250 275 3 00 325

T em perat ure (oC)

Akt

ivita

s (X

, S, Y

) %

Ko nversi E t ano lSelek t iv it as Aset aldeh idaYield Aset aldeh ida

5 0 % M o O 3 / TiO 2

CONCLUSION

The catalyst that loading of 50% MoO3 has higher intensity than 25% MoO3 . Both of the conversions and selectivities of MoO3 supported catalyst as a function of molybdenum loading and support. The highest conversion was 83% for the catalyst of 50%MoO3/TiO2, while the highest selectivity of acetaldehyde was 96% for the catalyst of 25%MoO3/SiO2. The highest of acetaldehyde yield was 51% by using MoO3/TiO2

suppoerted catalyst .

Katalis Industri

• Thanks you for your attention!