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Makalah (Code KKR 09)

Time on Stream Stability of H-ZSM-5 Catalyst on

Acetone Conversion to Aromatic ChemicalsDisampaikan dalam Forum Seminar Nasional Teknik KimiaPalembang, 19 Juli 2006

Oleh

Setiadi

[email protected]

[email protected]

SMS. 08159088431

Department Of Chemical EngineeringFaculty Of Engineering - University Of Indonesia
mailto:[email protected]:[email protected]:[email protected]:[email protected]


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Hidrokarbon

C1- C10Aseton

Aseton : senyawa organic

polar yang dapat diproduksi

dari materi hayati renewable

mll. fermentasi, pirolisis ,

maupun new process viasupercritical decomposition

Kemampuan shape-selectivity ZSM-5 terletak pada bangunan struktur kristalnya

yang diameter/bukaan pori sekitar 0,56 nm dan hampir homogen.

Katalis ZSM-5 banyak digunakan untuk transformasi reaksi-reaksi hidrokarbon

dibanding dgn. ZSM-5 digunakan reaksi senyawa organik polar

C1 : CH4 C2 : C2H4, C2H6

C3 : C3H6, C3H8 C4 : C4H8, C4H10

C5 : C5H10, C6 : C6H6, C6 alifatik

C7 : Toulena, Alifatik, C8 : Xylena,

alifatik C9 : Mesitylene (1,3,5 TMB)

C10 : Durene, Naphthalene

ZSM-5

Proses Katalitik


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H2O

Biomass

Materials

CO2

Fuel : LPG (C3-C4 H.Cs), Gasoline(C5-C10 H.Cs),

Diesel Fuel, Kerosene, Avian Jet Fuel, etc

Biomass

derived

liquid

Fotosintesis

Fossil ResourcesCrude Oils

(C1-C40) Hydrocarbons

Fuel Combustion

Waste

Transformation &

Utilization

Geological Time Frame

Process(Mil li ons years)

biological

activities

Biological time frame

The Concept Carbon Cycle Route for renewable biomass and non-renewable as the origins of

hydrocarbons for fuels & chemicals (developed from Kojima, 1998; Metzger & Eissen, 2004 dan Padabed et al.,2002)

CO2

Un-convertedCO2


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Fossil Resources

(Petroleum crude

Oil)

Refinery Process &

Catalytic Cracking

Unit (FCC)

Biomass

Materials

Biomass-derived liquid from

fermentation Products

(sagu, singkong, tetes tebu/molasses, 80 %Yield Limbah Tandan Kosong Sawit, dll.)

Renewable

Ethanol

Acetone,

Butanol

C1-C10

Aromatic

Compounds

Fuel (Gasohol),

(O.N., RVP)

Petrochemicals

Non-renewable

Resources

A Schematic Diagram of C1-C10 Hydrocarbons Route from the Origin

Target

Compounds

Biomass-Based Technology established ???

Catalytic Reaction Process? Catalyst ? HZSM-5 & Nat. Zeolite

Reaction condition?

Scope of this

Research Work

Minyak Nabati

( Sawit, Jarak, )


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A reaction mechanism for the acetone conversion for C3-C4 or C5-C10

Aromatichydrocarbons formation

O

H3C- C-CH=C(CH3)2

Mesityl oxide(MSO)

O OH

CH3 C CH2 C (CH3)2

Diacetone alcohol(DAA)

O

(H3C)2C=CHCCH=C(CH3)2

phorone ordiisopropylideneketone

O

2 [ H3C-C-CH3]

2 molecules of

Acetones

Self Aldol

condensationDehydration

- H2O

Further self Aldol

condensation

+ (CH3)2CO

- H2O

In progress of reaction: Continued con densation, forming

higher molecular weight species which may ac cumulate in

pore channel and shutting down the reaction

O

isophorone

Cracking inside the

Pores at higher

Temp > 350 oC

C3-C4 LPG

Acetic acid

1,3,5-

Trimethylbenzene

(Mesitylene)

Monoaromatic :

Benzene

Xylene

Toluene

EthylBenzene

C9

monoaromatic

C10

monoaromatic

Diaromatics :

Napthalene

Monomethylnaphthalene

Dimethylnapthalene

Trimetylnaphthalene

Tetramethylnapthalen

C5-C10 H.Cs of Gasoline(Shape Selective Formation)

Dimerization Condensation

Dehydrocyclization

Reaction at the external surface of ZSM-5

CH4

COx

H3C CH3C=HC O CH=C

H3C CH3C=CH-C-CH=C

H3C CH3C=HC CH=C

H3C CH3

Decomposition

Reaction at the internal or external surface of Zeolite

Reaction at the internal surface of ZSM-5


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Chang C.D dan A.J. Silvestri, 1977, The conversion of Methanol and Other O-Compounds to

hydrocarbons over Zeolite Catalysts,Journal of Catalysis, 47, 249-259Chang, Clarence D., W. H. Lang, and W.K. Bell, 1981, "Molecular Shape-Selective Catalysis in

Zeolite," in Catalysis of Organic Reactions edited by William R. Moser, Marcel Dekker Inc.,

73-94

Xu, Teng, Eric J. Munson, and James F. Haw, 1994, "Toward a Systematic Chemistry of Organic

Reactions in Zeolites: In Situ NMR Studies of Ketones," J. Am. Chem. Soc., 116, 1962-1972

Hutchings, Graham J., Peter Johnston, Darren F. Lee, Ali Stair Warwick, Craig D. Williams and

Mark Wilkinson, 1994, "The conversion of methanol and other O-compounds to hydrocarbons

over zeolite ",Journal of Catalysis 147, 177-185

Lucas, A., P. Canizares, A. Duran, A. Carrero, 1997, "Dealumination of HZSM-5 zeolites : Effect

of steaming on acidity and aromatization activity,"Appl. Catal. 154, 221

Stevens, Mark G., Denise Chen and Henry C. Foley, 1999, "Oxidized Cesium/Nanoporous Carbon

Materials: Solid-Base Catalysts with Highly Dispersed Active Sites,"J.C.S., Chemical

Commun., 275-276Dehertog, W.J.H., G.F. Fromen, 1999, "A catalytic route for aromatics production from LPG",

Applied Catalysis A: General189 63-75

Zaki, M.I., M. A. Hasan, F.A. Al-Sagheer, and L. Pasupulety, 2000, "Surface Chemistry of Acetone

on Metal Oxides: IR Observation of Acetone Adsorption and Consequent Surface Reactions on

Silica-Alumina versus Silica and Alumina,"Langmuir, 16, 430-436

Xu, M., W. Wang and Michael Hunger; 2003, " Formation of acetone enol on acidic zeolite ZSM-5

evidenced by H/D exchange", Chem Commun, 722-723

Tracking Acuan untuk MekanismeReaksi


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Shift Selectivities Due

to The Temp. Changes

Contoh :

2 (dua) Temp. 350 oC

& 400 oC untuk produk

Isobutene

Aromatics

Aliphatics

COx

(1,3,5 Trimetilbenzena)

Konversi Aseton & Sensitivitas Pergeseran Selektivitas Produk terhadap Suhu Reaksi

(Sumber : Chang, Lang, & Bell, 1981, Catalysis of Organic Reactions by William R. Moser (Editor),Marcel Dekker Inc., 73-94)


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The Framework of ZSM-5

structure

Ten-membered oxygenring structure

Zig-zags channel, Circularopenings 0.54 x 0.56 nm

Straight channel, Ellipticalopenings 0.51 x 0.55 nm

Secondary buildingblock, Chains of 5-membered oxygen rings

Vertically

-cross

sectional

view

Basic unit building

block-AlO4 or SiO4

tetrahedra structure

Secondary buildingblock, Chains of 5-membered oxygen

rings


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Ilustrasi difusi molekul

senyawa Hidrokarbon

diseputar mulut pori zeolit

(Source : Sierka and Sauer, J.

Phys. Chem. B2001, 105,

1603-1613)

Acidic protons migrate between the four oxygen atoms surrounding the tetrahedral

aluminum center in the following fashion (Ryder, dkk., J. Phys. Chem. B2000, 104, 6998)


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Zeolite Pore size, nm

Y 0.72

Mordenite 0.67 x 0.7

Offreite 0.64

ZSM-5 0.54 x 0.56

Ferrierite 0.43 x 0.55

Erionite 0.52 x 0.36

Pore Dimension for some Zeolites


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Objectives :

To observe the Performance of HZSM-5 on

Time on stream Stability (TOS) on the

Acetone Reaction to get the high as possible

acetone conversion, Aromatic Yield andProduct Selectivity

The influence of Si/Al ratio, Temperature

during TOS Catalytic Tests


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Batangan Baja SS 316

Reaktor Pipa, 10 mm

o.d., SS 316

19 cm

Lokasi Pengukuran

Suhu Unggun Katalis

35 cm

16 cm

Quartz Wool

Quartz sand

Termokope1

Unggun Katalis

Quartz Wool

6 mm , i.d

Reaktor Pipa, 10 mm

o.d., SS 316

Skema Diagram Penyusunan Katalisdalam Reaktor Pipa

N2

gas

Quartz sand

Mixture of ZSM-5 & quartz sand

Flow meter Pump

Stainless steel rod

Electric

furnace(1000W)

Pre-

heater

Ice - water bath

Gas product

Acetone

N2

liquid

drop

Acetone

fed by

pump

Experimental Method

Experimental Set-up for Catalytic Test

Wacetone??

Wproduk

cair??

Wproduk gas??


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Experimental conditions

Catalyst : H-ZSM-5

Origin : Japan (Commercial)

Si/Al ratio : 25 -100

Particle size (dp) : 3 meter

Weight of catalyst for bed : 1 gram

Quartz sand for blending : 5 gram (10-15 mesh)

Quartz sand for preheating : 7 gram (10-15 mesh)

Aceton (Cica) : min 99.5% purity

Carrier Gas : N2

Experimental Method


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Data GC-FID ( Hewlett Packard ) for Analysis of liquid product

The condition of GC-TCD for gaseous product

Column DB-1 (100 % DimethylPolysloxane), non-polar

60 m x 0.25 mm I.D., 0.25 (film) JW : 122-1062-JWCarrier Nitrogen

Oven 40 oC for 2 min; 40 - 220 oC with heating rate at 2.5 o C/min

Injector Split 1:100; 260 oC

Detector FID 290 oC Nitrogen make up gas sebesar 30 ml/min

Gas Chromatography GC 1 (organic) GC 2 (In-organic)

Column Porapaq Q Mol. Sieve

Carrier gas Helium Argon

Column Oven 80 oC 60 oC

Injection port 90 oC 80 oC

Detector (TCD) 90o

C 80o

C

Experimental Method


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Waktu retensi hasil deteksi chromatogram GC-FID kolom kapier DB-1

Posisi keberadaan Peak dikonfirmasi dgn.GC-MS Larutan Standard murni/ campuran

Peak No. Compounds Retention time, minute Calibration factor

1 Acetone ~6.25 2.2

2 C5-C6 Aliphatics 6.1-9.3 1

3 Benzene 7.98 1

4 Toluene (B.P. - 110.6 oC) 9.87 1

5 Ethylbenzene (B.P.136.3oC) 11.85 1

6 m+p-Xylene (B.P.137-138 oC) 12.1 1

7 o-Xylene (B.P. - 144 oC) 12.6 1

8 C9-Aromatics group* 13.8-15.6 1

9 C10-Aromatics** 16.6-17.7 1

10 Naphthalene - 18.5 111 MMN group- 20.5-21.0 1

12 DMN 22,3 1

13 TMN 23.3-24 1

* n-Propylbenzene, 1-Methyl-3-Ethylbenzene, 1-ethyl--Ethylbenzene, 1,3,5-Trimethylbenzene (Mesytylene), 1-

Methyl-2-Ethylbenzene, 1,2,4-Trimethylbenzene, 1,2,3-Trimethylbenzene

** 1,4-Diethylbenzene, n-butylbenzene, 1,2 diethylbenzene, 1,2,4,5-Tetramethylbenzene, 1,2,3,4-

Tetramethylbenzene

Experimental Method


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Experimental Method

Waktu retensi produk gas menggunakan GC-TCD

Peak Component Retention time, min Calibration

FactorPoropak - Q Mol.Sieve

1 CO2 0.9 0.91659

2 C2H4 1.4 0.87553

3 C2H6 1.8 0.80699

4 C3H6 5.2 0.67475

5 C4 12.8 0.56479

6 H2 1.7 0.10501

7 CH4 4.1 0.34531

8 CO 4.7 1.00367


17/33

Tipikal GC-FID Chromatogram sampel produk cair

Experimental Method

Un-reacted Acetone

C9-aromatik (Trimethylbenzene) , 13.8-15.6'

Toluene , 9.87

m+p-Xylene , 12.1

Benzene , 7.98'

Ethanol-AbsorbenC5-C6 aliph., 6.1-9.3

Ethylbenzene, 11.85O-Xylene,12.6'

C10-aromatik ,16.6-17.7

Methylnaphtahlene (MMN) , 20.5-21.0'

Naphthalene, 8.5

Dimethylnaphtahlene (DMN) , sekitar 22.3'Trimethylnaphtahlene (TMN), 23.3-24

Note

Kandungan Hidro-karbon dalam

sampel produk cair

juga telah dikonfir-

masi dengan GC-

Mass Spectrosmeter


18/33

Tipikal Chromatogram GC-TCD sampel produk gas

CH4

C4

CO

C3H8

H2

C2H6

C2H4

C3H6

N2Carrier gas

Chromatogram resulted from GCusing Molecular Sieve ColumnChromatogram resulted from GCusing Poropak Q Column

Experimental Method

M d P li iP hit k t F k i Li id F k i G


19/33

Aceton Feed 3cc during 34.5 min. Aceton Feed [mg] 2329.50

-1 = 1601 mg wt%(FID) Correction wt%(recalc) mg Product in Trap1 1641.41Acetone 0.373 0.8206 0.817 13.08 [mg]

C5~C

6 2.64 2.64 2.628 42.08

C6+-Aliphatics 8.68 8.68 8.641 138.35

Benzene 3.85 3.85 3.833 61.37

Toluene 23.14 23.14 23.037 368.83

Ethylbenzene 3.82 3.82 3.803 60.89m+p-Xylene 24.12 24.12 24.013 384.45

o-Xylene 7.27 7.27 7.238 115.88

C9-Aromatics 19.24 19.24 19.155 306.67

C10

-Aromatics 1.74 1.74 1.732 27.73

Naphthalene 1.33 1.33 1.324 21.20

2-Methylnaphthalene 1.21 1.21 1.205 19.29

1-Methylnaphthalene 0.17 0.17 0.169 2.71

Dimethylnaphthalene 1.92 1.92 1.911 30.60

Trimethylnaphthalene 0.495 0.495 0.493 7.89

Absorption Trap-2 : 9707 mgram Product in trap 2 [mg] 45.254Component Area FID Factor % w Component, mgEthanol 5156933.0 1.51E-07 7.79E-01 99.53 9661.746

Acetone 13091.8 1.53E-07 2.00E-03 0.26 24.848

Benzene 11702.5 6.913E-08 8.09E-04 0.10 10.037

Toluen 12089.5 6.913E-08 8.36E-04 0.11 10.369

Gas PhaseProducts Product Gas [mg] 642.84N2 rate 30 ml/min for 34.5 min vol/mmol 23.794872 ml/mmol

Vol. N2 1035 ml Nitrogen 43.496767 mmol

Component area Factor amount % mol mmol Mol. Weight mg

N2 1435406 1 1435406 73.94 43.50 28 1218H

2 196823 0.105096 20685 1.07 0.63 2 1

CO 17485 1.00367 17549 0.90 0.53 28 15

CO2 204423 0.916593 187373 9.65 5.68 44 250

CH4 37351 0.345307 12898 0.66 0.39 16 6

C2H

4 43612 0.875529 38184 1.97 1.16 28 32

C2H

6 8111 0.806991 6546 0.34 0.20 30 6

C3H6 61208 0.6747475 41300 2.13 1.25 42 53

C3H8 141126 0.652652 92106 4.74 2.79 44 123

C4+ Aliphatics 158055 0.564794 89269 4.60 2.71 58 157

Total output [mg] 2329.50

Acetone Conversion 98.37 % Liq. Oil Product Yield 72.40 wt %

Gas Product Yield 27.60 wt %

Metode Penelitia

% Carbon ?

% Carbon ?

% C ?

Perhitungan konv.aseton, Fraksi Liquid, Fraksi Gas


20/33

Experimental MethodSelectivities &YieldInterval of sample 0.58 h

Acetone conversion 98.37 %

Product composition

weight in g % weight % carbon

CO 14.89 0.67 0.31

CO2 249.83 11.21 3.31

CH4 6.25 0.28 0.23

C2H4 32.40 1.45 1.59

C2H6 5.95 0.27 0.29

C3H6 52.56 2.36 2.58

C3H8 122.81 5.51 6.03

C4+ Aliphatics 156.89 7.04 7.70C5~C6 Aliphatics 42.08 1.89 2.07

C6+-Aliphatics 138.35 6.21 6.79

Benzene 61.37 2.75 3.01

Toluene 368.83 16.54 18.11

Ethylbenzene 60.89 2.73 2.99

m+p-Xylene 384.45 17.24 18.87

o-Xylene 115.88 5.20 5.69

C9-Aromatics 306.67 13.75 15.05

C10-Aromatics 27.73 1.24 1.36

Naphthalene 21.20 0.95 1.04

2-Methylnaphthalene 19.29 0.87 0.95

1-Methylnaphthalene 2.71 0.12 0.13

DMN 30.60 1.37 1.50

TMN 7.89 0.35 0.39

2229.51 100.00 100.00

Selectivities by %C


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Results & Discussions

0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25 30

Time on stream [h]

Conversion[wt%

] Si/Al=25

Si/Al=75

Si/Al=100

Acetone conversion over HZSM-5 by various Si/Al mol ratio.

WHSV = 4 h-1, N2 carrier = 30 ml/min.

Si/Al=25, TOS =17 h stable at ca.100% Conv.

Si/Al=25

Si/Al=75

Si/Al=100


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0

10

20

30

4050

60

70

80

90100

0 5 10 15 20 25 30

Time on stream [h]

Conversion[wt%] 723 K

673 K

623 K

573 K

The stability of H-ZSM-5 Si/Al =25 on various reaction temperature

TOS


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0

20

40

60

80

100

0 5 10 15 20 25 30

Time on stream [h]

Monoaromaticyield[wt%

]723 K

673 K

623 K

573 K

Yield of monoaromatic duing time on stream on various temperature

TOS < 13 h, Yield > 60%



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0 25 50

CO

CO2

CH4

C2H4

C2H6

C3H6

C3H8

C4 aliphatics

C5~C6 aliphatics

C6+ aliphatics

Benzene

Toluene

Ethylbenzene

m+p-Xylene

o-Xylene

C9-Aromatics

C10-Aromatics

Naphthalene

2-Methylnaphthalene

1-Methylnaphthalene

Dimethylnaphthalene

Trimethylnaphthalene

Selectivity (% carbon)

TOS = 40 min

TOS = 70 min

TOS = 100 min

Product Selectivity within 100 min

with H-ZSM-5 Si/Al=25

Diaromatik

COx

Monoiaromatik

Alifatik

H-ZSM-5 High Shape

Selective for Aromatic

Formations, Total Select.

> 60 %



25/33

Si/Al=25, T=673 K

0

20

40

60

80

10 0

0 10 20 30

Time on stream [h]

Selectivity[%Ca

rbon]

Si/Al=75, T=673K

0

20

40

60

80

10 0

0 10 20 30 40

Time on stream [h]

Selectivity[%

Car

bon]

Si /Al=100 and T= 673K

0

20

40

60

80

100

0 10 20 30

Time on stream [h ]

Selectivity[%Ca

rbon]

Fig. 6 The change of monoaromatic and C4 aliphatics selectivity

during the progressing of time on stream reaction

NoteThe relative symmetry in the opposite direction between the increasing of C4

aliphatics and the decreasing of monoaromatic selectivity

The shift selectivity between the change of monoaromatic and C4 aliphatics

selectivity during TOS

Monoiaromatik

C4 Aliphatics

Monoiaromatik

Monoiaromatik

C4 Aliphatics C4 Aliphatics



26/33

ConclusionsZSM-5 with Si/Al = 25 is the high active and stable than the

Si/Al ratio, it indicates that the reaction of acetone reaction

required a high acid density on the surface of catalyst.

The reaction on 673 K is a favorable temperature for

acetone conversion toward aromatic products. The lowertemperatures of reaction lead to rapid deactivation, and the

higher temperatures tend to decline the yield/selectivity of

aromatics products

The formation of aromatic compounds come from the C4

aliphatics and big possibilities that the loss of activity of

catalyst and shift selectivity are caused by coking which

covers the surface acid sites of ZSM-5


27/33


28/33

Terima kasih kpd.

Prof. T. Kojima, Staffs & the Excellent Students,Faculty Engineering, Seikei University, Tokyo-Japan

Prof. T. TsutsuiApplied Chemistry & Chem. Engineering,Kagoshima University, Kyushu-Japan

Prof. Takao Masuda,Div. of Material Science and Eng., Graduate Schoolof Eng., Hokkaido University, Sapporo, Japan


29/33

The surface area for fresh and used catalyst

Catalyst

Total area,

m2/g

Micropore area,

m2/g

HZSM-5 Fresh 321.8 209.4

Used 225.4 159.9

HNZ (protonated Nat.

Zeolite)

Fresh 294.4 248.2

Used 235.3 155.8

15 wt%B2O3-HNZ Fresh 115.4 58.3

Used 76.0 44.2


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The powder of Fresh Catalyst, the white color

The change of color for the powder of used Catalyst to be black or dark brown


31/33

Effect of Boron oxide loading into HNZ catalyst on Product Reaction

CatalystHNZ

5 wt%

B2O

3-HNZ

15 wt%B2O3-

HNZ

25 wt%B2O

3-

HNZ

Temperature [oC] 400 400 400Conversion [%] 98.9 98.4 95.8 20.3

Product distribution (% w)CO 0.31 0.63 0.65 0.36

CO2 2.93 3.66 5.45 4.85

CH4 0.21 0.27 0.30 0.10

C2H4 1.0 2.96 4.11 0.17

C2H6 0.31 0.24 0.10 0.00

C3H6 1.55 5.82 12.60 1.26C3H8 6.90 4.02 1.84 0.00

C4 aliphatics 7.35 9.69 20.3061.70

C3-C4 Hydrocarbons 15.80 19.53 34.74 62.96

Liquid Hydrocarbon 77.30 72.80 54.70 31.50


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Feed Acetone acetone + H2O

(50% wt add)

Temperature, [oC] 400 400

LHSV [h-1] 2.18 4.32

Conversion [%] 98.9 99.1

Product (wt %)

Benzene 5.64 4.24

Toluene 21.12 18.26

Ethylbenzene 1.44 1.79

m+p-Xylene 15.38 16.01

o-Xylene 4.67 4.9

C9-Aromatics 7.22 9.36

Naphthalene 0.49 0.65

2-Methylnaphthalene 1.64 1

1-Methylnaphthalene 0.59 0.32

Dimethylnaphthalene 1.83 1.17

Trimethylnaphthalene 0.16 0.24

The comparation of the results due to the water addition into acetone feed


33/33

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time on stream [h]

A

cetoneconversion,

%

-1

0

1

2

3

4

5

6

Paraffin/Olefinratio

Si/Al=25

Paraf fin/Ol

efin

The change of acetone conversion along with Paraffin/olefin ratio during reaction

over ZSM-5 (Si/Al=25)

Reaction condition : Temperature = 673 K, P=0.13 MPa, WHSV= 4 g/g.h, N2 carrier

= 30 ml/min

Documents

01 AcetoneConverison SETIADI SNTKI Plmbang 19Juli 06