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
Proses Katalitik
Aseton
Aseton : senyawa organic
polar yang dapat diproduksi
dari materi hayati renewable
mll. fermentasi, pirolisis ,
maupun new process via
supercritical decomposition
ZSM-5
Hidrokarbon
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
Geological Time Frame
Process (Millions years)
Biomass
derived
liquid
Fossil Resources – Crude Oils
(C1-C40) Hydrocarbons
Biological time frame
Transformation &
Utilization
Fuel : LPG (C3-C4 H.Cs), Gasoline(C5-C10 H.Cs),
Diesel Fuel, Kerosene, Avian Jet Fuel, etc
Biomass
Materials
Fuel Combustion
Waste
biological
activities
Fotosintesis
CO2
H2O
CO2
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)
Resources
Non-renewable
Fossil Resources
(Petroleum crude
Oil)
Scope of this
Research Work
Target
Compounds
Refinery Process &
Catalytic Cracking
Unit (FCC)
C1-C10
Aromatic
Compounds
Renewable
 Fuel (Gasohol),
(O.N., RVP)
 Petrochemicals
Ethanol
Acetone,
Butanol
Biomass
Materials
•Minyak Nabati
( Sawit, Jarak, )
Biomass-derived liquid from
fermentation Products
(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
Reaction at the internal or external surface of Zeolite
O
║
2 [ H3C-C- CH3]
Self Aldol
condensation
2 molecules of
Acetones
Acetic acid
Decomposition
CH4
COx
O
OH
║
│
CH3 C CH2 C (CH3)2
Mesityl oxide
(MSO)
Diacetone alcohol
(DAA)
Further self Aldol
condensation
+ (CH3)2CO
- H2O
Cracking inside the
Pores at higher
Temp > 350 oC
C3-C4 LPG
O
║
(H3C)2C=CHCCH=C(CH3)2
phorone or
diisopropylideneketone
O
Dimerization Condensation –
Dehydrocyclization
C5-C10 H.Cs of Gasoline
(Shape Selective Formation)
Monoaromatic :
Benzene
Xylene
Toluene
EthylBenzene
C9 monoaromatic
C10monoaromatic
O
║
H3C- C-CH=C(CH3)2
Dehydration
- H2O
In progress of reaction: Continued condensation, forming
higher molecular weight species which may accumulate in
pore channel and shutting down the reaction
isophorone
Diaromatics :
Napthalene
Monomethylnaphthalene
Dimethylnapthalene
Trimetylnaphthalene
Tetramethylnapthalen
Reaction at the internal surface of ZSM-5
H3C
CH3
O
CH=C
H3C
║
CH3
C=CH-C-CH=C
H3C
CH3
C=HC
CH=C
H3C
CH3
C=HC
1,3,5Trimethylbenzene
(Mesitylene)
Reaction at the external surface of ZSM-5
A reaction mechanism for the acetone conversion for C3-C4 or C5-C10
Aromatic hydrocarbons formation
Tracking Acuan untuk Mekanisme Reaksi
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
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
block-AlO4 or SiO4
tetrahedra structure
Ten-membered oxygen
ring structure
Secondary building
block, Chains of 5membered oxygen rings
Secondary building
block, Chains of 5membered oxygen
rings
Vertically
-cross
sectional
view
Straight channel, Elliptical
openings 0.51 x 0.55 nm
Zig-zags channel, Circular
openings 0.54 x 0.56 nm
The Framework of ZSM-5
structure
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
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
Preheater
Acetone
fed by
pump
Acetone
19 cm
Quartz sand
liquid
drop
Quartz Wool
Quartz sand
Electric
furnace
(1000W)
N2
gas
Termokope1
Unggun Katalis
Mixture of ZSM-5 & quartz sand
16 cm
Lokasi Pengukuran
Suhu Unggun Katalis
Stainless steel rod
Quartz Wool
Batangan Baja SS 316
Wproduk
cair??
35 cm
Reaktor Pipa, 10 mm
o.d., SS 316
Gas product
Ice - water bath
Wproduk gas??
Experimental Set-up for Catalytic Test
Skema Diagram Penyusunan Katalis
dalam Reaktor Pipa
Experimental Method
Experimental conditions
Catalyst
Origin
: H-ZSM-5
: Japan (Commercial)
Si/Al ratio
Particle size (dp)
Weight of catalyst for bed
: 25 -100
: 3 meter
: 1 gram
Quartz sand for blending
Quartz sand for preheating
Aceton (Cica)
: 5 gram (10-15 mesh)
: 7 gram (10-15 mesh)
: 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), 1Methyl-2-Ethylbenzene, 1,2,4-Trimethylbenzene, 1,2,3-Trimethylbenzene
** 1,4-Diethylbenzene, n-butylbenzene, 1,2 diethylbenzene, 1,2,4,5-Tetramethylbenzene, 1,2,3,4Tetramethylbenzene
Experimental Method
Waktu retensi produk gas menggunakan GC-TCD
Peak
Component
Retention time, min
Poropak - Q
Mol.Sieve
Calibration
Factor
1
CO2
0.9
0.91659
2
C 2 H4
1.4
0.87553
3
C2H6
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-Absorben
Un-reacted Acetone
C5-C6 aliph., 6.1-9.3‘
Benzene , 7.98'
Toluene , 9.87‘
Ethylbenzene, 11.85‘
m+p-Xylene , 12.1‘
O-Xylene,12.6'
C10-aromatik ,16.6-17.7‘
C9-aromatik (Trimethylbenzene) , 13.8-15.6'
Naphthalene, 8.5‘
Methylnaphtahlene (MMN) , 20.5-21.0'
Dimethylnaphtahlene (DMN) , sekitar 22.3'
Trimethylnaphtahlene (TMN), 23.3-24
Tipikal GC-FID Chromatogram sampel produk cair
Note
Kandungan Hidrokarbon dalam
sampel produk cair
juga telah dikonfirmasi dengan GCMass Spectrosmeter
Experimental Method
Tipikal Chromatogram GC-TCD sampel produk gas
C2H4
H2
N2 –Carrier gas
C2H6
CH4
C3H6
CO
C3H8
C4
Chromatogram resulted from GC
using Poropak Q Column
Chromatogram resulted from GC
using Molecular Sieve Column
Perhitungan konv.aseton, Fraksi Liquid, Fraksi Gas
Aceton Feed
Ｔｒａｐ-1 = 1601 mg
Acetone
C5~C6
C6+-Aliphatics
Benzene
Toluene
Ethylbenzene
m+p-Xylene
o-Xylene
C9-Aromatics
C10-Aromatics
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Dimethylnaphthalene
Trimethylnaphthalene
Absorption Trap-2 :
Component
Ethanol
Acetone
Benzene
Toluen
3cc during 34.5 min.
wt%
(FID)
0.373
2.64
8.68
3.85
23.14
3.82
24.12
7.27
19.24
1.74
1.33
1.21
0.17
1.92
0.495
9707
Area
5156933.0
13091.8
11702.5
12089.5
Correction
0.8206
2.64
8.68
3.85
23.14
3.82
24.12
7.27
19.24
1.74
1.33
1.21
0.17
1.92
0.495
mgram
FID Factor
1.51E-07
1.53E-07
6.913E-08
6.913E-08
30
1035
area
1435406
196823
17485
204423
37351
43612
8111
61208
141126
158055
ml/min for
ml
Factor
1
0.105096
1.00367
0.916593
0.345307
0.875529
0.806991
0.6747475
0.652652
0.564794
wt%(recalc)
0.817
2.628
8.641
3.833
23.037
3.803
24.013
7.238
19.155
1.732
1.324
1.205
0.169
1.911
0.493
mg
13.08
42.08
138.35
61.37
368.83
60.89
384.45
115.88
306.67
27.73
21.20
19.29
2.71
30.60
7.89
7.79E-01
2.00E-03
8.09E-04
8.36E-04
%w
99.53
0.26
0.10
0.11
Acetone Conversion
Gas Product Yield
98.37
27.60
34.5
amount
1435406
20685
17549
187373
12898
38184
6546
41300
92106
89269
%
wt %
min
% mol
73.94
1.07
0.90
9.65
0.66
1.97
0.34
2.13
4.74
4.60
Aceton Feed [mg]
2329.50
Product in Trap1
[mg]
1641.41
% Carbon ?
Product in
Component, mg
9661.746
24.848
10.037
10.369
Gas
Phase
Products
N2 rate
Vol. N2
Component
N2
H2
CO
CO2
CH4
C2H4
C2H6
C3H6
C3H8
C4+ Aliphatics
Metode Penelitian
vol/mmol
Nitrogen
mmol
43.50
0.63
0.53
5.68
0.39
1.16
0.20
1.25
2.79
2.71
Liq. Oil Product Yield
trap 2 [mg]
45.254
% Carbon ?
Product Gas [mg]
23.794872
43.496767
Mol. Weight
28
2
28
44
16
28
30
42
44
58
Total output [mg]
72.40
642.84
ml/mmol
mmol
mg
1218
1
15
250
6
32
6
53
123
157
2329.50
wt %
%C?
Selectivities &Yield
Experimental Method
0.58
98.37
Interval of sample
Acetone conversion
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
DMN
TMN
weight in g
14.89
249.83
6.25
32.40
5.95
52.56
122.81
156.89
42.08
138.35
61.37
368.83
60.89
384.45
115.88
306.67
27.73
21.20
19.29
2.71
30.60
7.89
2229.51
Product composition
% weight
0.67
11.21
0.28
1.45
0.27
2.36
5.51
7.04
1.89
6.21
2.75
16.54
2.73
17.24
5.20
13.75
1.24
0.95
0.87
0.12
1.37
0.35
100.00
h
%
% carbon
0.31
3.31
0.23
1.59
0.29
2.58
6.03
7.70
2.07
6.79
3.01
18.11
2.99
18.87
5.69
15.05
1.36
1.04
0.95
0.13
1.50
0.39
100.00
Selectivities by %C
Si/Al=25, TOS =17 h stable at ca.100% Conv.
Results & Discussions
Conversion [wt%]
100
90
Si/Al=100
80
Si/Al=25
Si/Al=25
Si/Al=75
70
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 & Discussions
Conversion [wt%]
TOS <= 17 h stable at ca.100% Conv.
100
90
80
70
60
50
40
30
20
10
0
723 K
673 K
623 K
573 K
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 & Discussions
Monoaromatic yield [wt%]
100
723 K
673 K
80 TOS < 13 h, Yield > 60%
623 K
60
573 K
40
20
0
0
5
10
15
20
25
30
Time on stream [h]
Yield of monoaromatic duing time on stream on various temperature
Results & Discussions
Trimethylnaphthalene
TOS = 40 min
Dimethylnaphthalene
Diaromatik
TOS = 70 min
1-Methylnaphthalene
2-Methylnaphthalene
TOS = 100 min
Naphthalene
C10-Aromatics
H-ZSM-5 → High Shape
Selective for Aromatic
Formations, Total Select.
> 60 %
C9-Aromatics
Monoiaromatik
o-Xylene
m+p-Xylene
Ethylbenzene
Toluene
Benzene
C6+ aliphatics
C5~C6 aliphatics
C4 aliphatics
Alifatik
C3H8
C3H6
C2H6
C2H4
Product Selectivity within 100 min
with H-ZSM-5 Si/Al=25
CH4
COx
CO2
CO
0
25
Selectivity (% carbon)
50
Results & Discussions
100
100
Monoiaromatik
60
40
C4 Aliphatics
20
80
Selectivity [ % Carbon]
100
80
Monoiaromatik
60
40
C4 Aliphatics
20
0
0
0
10
20
Time on stre am [h]
30
Si/Al=100 and T= 673K
Si/Al=75, T=673K
Selectivity [ % Carbon]
Selectivity [ % Carbon]
Si/Al=25, T=673 K
Monoiaromatik
80
60
40
20
C4 Aliphatics
0
0
10
20
30
Time on stre am [h]
40
0
10
20
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 C4 aliphatics
selectivity during TOS
30
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, TokyoJapan
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,
m2/g
Micropore area,
m2/g
Fresh
321.8
209.4
Used
225.4
159.9
Fresh
294.4
248.2
Used
235.3
155.8
Fresh
115.4
58.3
Used
76.0
44.2
Catalyst
HZSM-5
HNZ (protonated Nat.
Zeolite)
15 wt%B2O3-HNZ
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
25 wt%B2O3HNZ
HNZ
5 wt%
B2O3-HNZ
15 wt%B2O3HNZ
Temperature [oC]
400
400
400
Conversion
98.9
98.4
95.8
20.3
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
Catalyst
[%]
Product distribution (% w)
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
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
Product (wt %)
6
100.0
5
Si/Al=25
80.0
4
70.0
60.0
3
Paraffin/Ol
efin
50.0
40.0
30.0
2
1
20.0
Paraffin/Olefin ratio
Acetone conversion, %
90.0
0
10.0
-1
0.0
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