Makalah (Code KKR 09)

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

Acetone Conversion to Aromatic Chemicals

Disampaikan dalam Forum Seminar Nasional Teknik Kimia

Palembang, 19 Juli 2006

Oleh

Setiadi
setiadi@che.ui.edu or
hasbila@eng.ui.ac.id
SMS. 08159088431

Department Of Chemical Engineering

Faculty Of Engineering - University Of Indonesia
 Introduction

Aseton
Aseton : senyawa organic
polar yang dapat diproduksi
dari materi hayati renewable
mll. fermentasi, pirolisis ,
maupun new process via
supercritical decomposition
Proses
Katalitik Hidrokarbon
ZSM-5
C1- C10
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

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
 Non-Renewable Introduction
Route
Geological Time Frame
Process (Millions years)

Renewable Route
Biomass Fossil Resources – Crude Oils

(The Yellow
derived (C1-C40) Hydrocarbons

Arrows)
liquid
Transformation &
Biological time frame Utilization

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

Biomass
Diesel Fuel, Kerosene, Avian Jet Fuel, etc
Materials

biological Fuel Combustion

activities Waste

Fotosintesis
CO2 CO2

H2O Un-converted CO2

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)
 Introduction

Resources
Non-renewable Renewable

Fossil Resources
(Petroleum crude  Fuel (Gasohol), Biomass
Oil) (O.N., RVP) Materials
 Petrochemicals
Scope of this
Refinery Process & •Minyak Nabati
Catalytic Cracking
Research Work Unit (FCC) ( Sawit, Jarak, )
C1-C10
Target Ethanol Biomass-derived liquid from
Aromatic
Compounds Acetone, fermentation Products
Compounds
Butanol (sagu, singkong, tetes tebu/molasses,
80 % Yield Limbah Tandan Kosong
Sawit, dll.)

Biomass-Based Technology established ???

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

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

 Fundamental
Reaction at the internal or external surface of Zeolite
Review
O Self Aldol O OH Dehydration O
condensation ║
║ ║ │ - H2O H3C- C-CH=C(CH3)2
2 [ H3C-C- CH3] CH3 C CH2 C (CH3)2

2 molecules of Diacetone Mesityl oxide

Acetones alcohol (MSO)
Further self Aldol
(DAA) condensation
+ (CH3)2CO
- H2O
Cracking inside the
O
Pores at higher ║
Acetic acid Temp > 350 oC (H3C)2C=CHCCH=C(CH3)2

phorone or
diisopropylideneketone
Decomposition C3-C4 LPG O

CH4
Dimerization Condensation –
Dehydrocyclization In progress of reaction: Continued condensation,
COx forming higher molecular weight species which
may accumulate in pore channel and shutting
down the reaction
C5-C10 H.Cs of Gasoline
(Shape Selective Formation) isophoron
Monoaromatic : Diaromatics : e
H3 C CH3
Benzene Napthalene
Xylene C=HC O CH=C
Monomethylnaphthalene
Toluene H3 C ║ CH3
Dimethylnapthalene
EthylBenzene Trimetylnaphthalene
C9 monoaromatic Tetramethylnapthalen
1,3,5-
Trimethylbenzene C=CH-C-CH=C
C10monoaromatic
(Mesitylene) H3 C CH3
C=HC CH=C
H3 C CH3

Reaction at the internal surface of ZSM-5 Reaction at the external surface of ZSM-5

A reaction mechanism for the acetone conversion for C 3-C4 or C5-C10

Aromatic hydrocarbons formation
 Fundamental
Tracking Acuan untuk Mekanisme Reaksi Review

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, 249-259
Chang, 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 β", 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., 275-276
Dehertog, W.J.H., G.F. Fromen, 1999, "A catalytic route for aromatics production from LPG",
Applied Catalysis A: General 189 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
 Fundamental
Review
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)
Basic unit building
Fundamental
block-AlO4 or SiO4 Review
tetrahedra structure
Ten-membered
oxygen ring structure
Secondary building
block, Chains of 5-
membered oxygen rings
Secondary building
block, Chains of 5-
membered oxygen Straight channel, Elliptical
rings openings 0.51 x 0.55 nm

Verticall
y-cross
sectional
Zig-zags channel, Circular
view openings 0.54 x 0.56 nm

The Framework of ZSM-5

structure
 Fundamental
Review
Acidic protons migrate between the four oxygen atoms surrounding the tetrahedral
aluminum center in the following fashion (Ryder, dkk., J. Phys. Chem. B 2000, 104, 6998)

(Source : Sierka and Sauer, J.

Phys. Chem. B 2001, 105,
1603-1613)

Ilustrasi difusi molekul

senyawa Hidrokarbon
diseputar mulut pori zeolit
 Fundamental
Review
Pore Dimension for some Zeolites
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

 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 and
Product Selectivity

• The influence of Si/Al ratio, Temperature

during TOS Catalytic Tests
 Experimental Method

Wacetone??
6 mm , i.d

N2

Flow meter Pump Acetone

fed by 19 cm Termokope1
Pre- pump
heater Acetone Quartz sand
liquid
drop
Quartz Wool
Quartz sand
Electric Unggun Katalis
furnace Mixture of ZSM-5 & quartz sand 16 cm
(1000W) Lokasi Pengukuran
Suhu Unggun Katalis

N2 Stainless steel rod

gas Quartz Wool

Batangan Baja SS 316

Wproduk cair??
35 cm
Reaktor Pipa, 10 mm
o.d., SS 316

Gas product
Wproduk gas??
Ice - water bath
Skema Diagram Penyusunan Katalis
dalam Reaktor Pipa
Experimental Set-up for Catalytic Test
 Experimental Method

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
Data GC-FID ( Hewlett Packard ) for Analysis of liquid product
Column DB-1 (100 % DimethylPolysloxane), non-polar
60 m x 0.25 mm I.D., 0.25 μ (film) JW : 122-1062-JW
Carrier 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

The condition of GC-TCD for gaseous product

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) 90 oC 80 oC
 Experimental Method
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 1
11 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-
 Experimental Method

Waktu retensi produk gas menggunakan GC-TCD

Peak Component Retention time, min Calibration

Poropak - Q Mol.Sieve Factor

1 CO2 0.9 0.91659

2 C 2 H4 1.4 0.87553
3 C 2 H6 1.8 0.80699
4 C 3 H6 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
 Experimental Method
Ethanol- Un-reacted
Absorben Acetone
C5-C6 aliph., 6.1-9.3‘
Benzene ,
7.98'

Toluene ,
9.87‘

Ethylbenzene,
11.85‘ m+p-Xylene ,
O- 12.1‘
Xylene,12.6'

C10-aromatik ,16.6-
17.7‘ C9-aromatik (Trimethylbenzene) ,
13.8-15.6' Note
Naphthalene,
8.5‘ Kandungan Hidro-
Methylnaphtahlene (MMN) , 20.5-
karbon dalam
21.0' sampel produk cair
Dimethylnaphtahlene (DMN) , juga telah dikonfir-
sekitar 22.3' masi dengan GC-
Trimethylnaphtahlene (TMN), 23.3-
24
Mass Spectrosmeter

Tipikal GC-FID Chromatogram sampel produk cair

 Experimental Method

Tipikal Chromatogram GC-TCD sampel produk gas

H2
C2H4 N2 –Carrier gas
C2H6
CH4
C3H6
CO

C3H8

C4

Chromatogram resulted Chromatogram resulted

from GC using Poropak Q from GC using Molecular
Column Sieve Column
 Perhitungan konv.aseton, Fraksi Liquid, Fraksi Gas Metode Penelitian
Aceton Feed 3cc during 34.5 min. Aceton Feed [mg] 2329.50
Ｔｒａｐ -1 = 1601 mg wt%
(FID) Correction wt%(recalc) mg Product in Trap1 1641.41
Acetone 0.373 0.8206 0.817 13.08 [mg]
C5~C6 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 % Carbon ?
Ethylbenzene 3.82 3.82 3.803 60.89
m+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
% Carbon ?
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] 45.254
Component Area FID Factor %w Component, mg
Ethanol 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
%C?
Toluen 12089.5 6.913E-08 8.36E-04 0.11 10.369
Gas Phase
Products Product Gas [mg] 642.84
N2 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
Selectivities &Yield Experimental Method
Interval 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 7.70
C5~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 Selectivities by %C
0.35 0.39
Si/Al=25, TOS =17 h stable at ca.100% Conv.
Results &
Discussions
100
Si/Al=25
Conversion [wt%]
90
Si/Al=25
80 Si/Al=100
70 Si/Al=75

60 Si/Al=75
Si/Al=100
50
40
30
20
10
0
0 5 10 15 20 25 30
Time on stream [h]

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

WHSV = 4 h-1, N2 carrier = 30 ml/min.
 Results &
TOS <= 17 h stable at ca.100% Conv. Discussions
100
723 K
90
Conversion [wt%]

80 673 K
70 T=
67 623 K
60 3
K
50 573 K
40
T= T= 72 3
30 K
57 T= 62 3
20 3K K
10
0
0 5 10 15 20 25 30

Time on stream [h]

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

 Results &
100
Discussions
723 K
673 K
80 TOS < 13 h, Yield > 60%
623 K
Monoaromatic yield [wt%]

60 573 K

T=
67
3K
40 T= 7 2 3
K

20

T = 57 T= 62 3
0 3K K
0 5 10 15 20 25 30

Time on stream [h]

Yield of monoaromatic duing time on stream on various temperature

 Results &
Trimethylnaphthalene

Discussions
TOS = 40 min
Dimethylnaphthalene
Diaromatik 1-Methylnaphthalene TOS = 70 min

2-Methylnaphthalene
TOS = 100 min
Naphthalene
C10-Aromatics
C9-Aromatics H-ZSM-5 → High
o-Xylene
Monoiaromati m+p-Xylene
Shape Selective for
k Ethylbenzene Aromatic Formations,
Toluene
Benzene
Total Select.
C6+ aliphatics > 60 %
C5~C6 aliphatics
C4 aliphatics

Alifatik C3H8
C3H6
C2H6
C2H4
CH4
Product Selectivity within 100 min
CO2
COx CO
with H-ZSM-5 Si/Al=25
0 25 50
Selectivity (% carbon)
 Results &
100
Si/Al=25, T=673 K Discussions
Si/Al=75, T=673K
100
Si/Al=100 and T= 673K

100

Selectivity [ % Carbon]
Selectivity [ % Carbon]

Selectivity [ % Carbon]
80 Monoiaromati 80 80 Monoiaromati
k Monoiaromati k
60 60 60
k
40 40 40

20 C4 Aliphatics 20 C4 Aliphatics 20
C4 Aliphatics
0 0 0

0 10 20 30 0 10 20 30 40 0 10 20 30
Time on stream [h] Time on stre am [h]
Time on stre am [h]

Fig. 6 The change of monoaromatic and C4 aliphatics selectivity

during the progressing of time on stream reaction

Note
•The 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 C 4 aliphatics

selectivity during TOS
 Conclusions
•ZSM-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 lower
temperatures 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
Terima kasih kpd.
Prof. T. Kojima, Staffs & the Excellent
Students, Faculty Engineering, Seikei
University, Tokyo-Japan
Prof. T. Tsutsui
Applied Chemistry & Chem. Engineering,
Kagoshima University, Kyushu-Japan
Prof. Takao Masuda,
Div. of Material Science and Eng., Graduate
School of Eng., Hokkaido University,
Sapporo, Japan
 The surface area for fresh and used catalyst
Total area, Micropore area,
Catalyst m2/g m2/g

HZSM-5 Fresh 321.8 209.4

Used 225.4 159.9

HNZ (protonated Nat. Fresh 294.4 248.2

Zeolite)
Used 235.3 155.8

15 wt%B2O3-HNZ Fresh 115.4 58.3

Used 76.0 44.2

 The powder of Fresh Catalyst, the white color

The change of color for the powder of used Catalyst to be black or dark brown
 Effect of Boron oxide loading into HNZ catalyst on Product Reaction

5 wt% 15 wt%B2O3- 25 wt%B2O3-

HNZ B2O3-HNZ
Catalyst HNZ HNZ
Temperature [oC] 400 400 400
Conversion [%] 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 1.26
C3H8 6.90 4.02 1.84 0.00
C4 aliphatics 7.35 9.69 20.30 61.70
C3-C4 Hydrocarbons 15.80 19.53 34.74 62.96
Liquid Hydrocarbon 77.30 72.80 54.70 31.50
The comparation of the results due to the water addition into acetone feed
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
 100.0 6
90.0
Si/Al=25 5
80.0

Paraffin/Olefin ratio
Acetone conversion, %

70.0 4
60.0
3
50.0 Paraffin/Ol
efin
40.0 2
30.0 1
20.0
0
10.0
0.0 -1
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time on stream [h]

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