makalah (code kkr 09) time on stream stability of h-zsm-5 catalyst on acetone conversion to aromatic...
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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
[email protected] or [email protected]. 08159088431
Department Of Chemical EngineeringFaculty Of Engineering - University Of Indonesia
Hidrokarbon
C1- C10
AsetonAseton : senyawa organic polar yang dapat diproduksi dari materi hayati renewable mll. fermentasi, pirolisis , maupun new process via supercritical 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, C2H6C3 : 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
Introduction
Non-Renewable Route
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 Resources – Crude Oils(C1-C40) Hydrocarbons
Fuel Combustion Waste
Transformation & Utilization
Geological Time Frame Process (Millions 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)
Ren
ew
ab
le
Rou
te
(Th
e Y
ellow
A
rrow
s)
CO2
Un-converted CO2
Introduction
Introduction
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
EthanolAcetone, 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, )
A reaction mechanism for the acetone conversion for C3-C4 or C5-C10
Aromatic hydrocarbons 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 or diisopropylideneketone
O ║
2 [ H3C-C- CH3]
2 molecules of
Acetones
Self Aldol condensation
Dehydration - H2O
Further self Aldol condensation + (CH3)2CO - H2O
In progress of reaction: Continued condensation, forming higher
molecular weight species which may accumulate 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-Trimethylbe
nzene(Mesitylene)
Monoaromatic :BenzeneXyleneToluene
EthylBenzeneC9 monoaromaticC10monoaromatic
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
CH4COx
H3C CH3
C=HC O CH=C H3C ║ CH3 C=CH-C-CH=C H3C CH3
C=HC CH=CH3C CH3
Decomposition
Reaction at the internal or external surface of Zeolite
Reaction at the internal surface of ZSM-5
Fundamental 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
Tracking Acuan untuk Mekanisme Reaksi
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)
Fundamental Review
The Framework of ZSM-5 structure
Ten-membered oxygen ring structure
Zig-zags channel, Circular openings 0.54 x 0.56 nm
Straight channel, Elliptical openings 0.51 x 0.55 nm
Secondary building block, Chains of 5-membered oxygen rings
Vertically-cross sectional view
Basic unit building block-AlO4 or SiO4 tetrahedra structure
Secondary building block, Chains of 5-membered oxygen
rings
Fundamental Review
Ilustrasi difusi molekul senyawa Hidrokarbon diseputar mulut pori zeolit
(Source : Sierka and Sauer, J. Phys. Chem. B 2001, 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. B 2000, 104, 6998)
Fundamental Review
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
Fundamental Review
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
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 Katalis dalam 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??
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
The condition of GC-TCD for gaseous product
Column DB-1 (100 % DimethylPolysloxane), non-polar60 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
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-Tetramethylbenzene
Experimental Method
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
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-Absorben
C5-C6 aliph., 6.1-9.3‘
Ethylbenzene, 11.85‘
O-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
Tipikal Chromatogram GC-TCD sampel produk gas
CH4
C4
CO
C3H8
H2
C2H6
C2H4
C3H6
N2 –Carrier gas
Chromatogram resulted from GC using Molecular Sieve Column
Chromatogram resulted from GC using Poropak Q
Column
Experimental Method
Aceton Feed 3cc during 34.5 min. Aceton Feed [mg] 2329.50Trap -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
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
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 7.89Absorption 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
Toluen 12089.5 6.913E-08 8.36E-04 0.11 10.369Gas Phase Products 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 1218
H2 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
C2H4 43612 0.875529 38184 1.97 1.16 28 32
C2H6 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 157Total output [mg] 2329.50
Acetone Conversion 98.37 % Liq. Oil Product Yield 72.40 wt %
Gas Product Yield 27.60 wt %
Metode Penelitian
% Carbon ?
% Carbon ?
% C ?
Perhitungan konv.aseton, Fraksi Liquid, Fraksi Gas
Experimental MethodSelectivities &YieldInterval of sample 0.58 h
Acetone conversion 98.37 %
Product composition
weight in g % weight % carbonCO 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 6.79Benzene 61.37 2.75 3.01Toluene 368.83 16.54 18.11Ethylbenzene 60.89 2.73 2.99m+p-Xylene 384.45 17.24 18.87o-Xylene 115.88 5.20 5.69
C9-Aromatics 306.67 13.75 15.05
C10-Aromatics 27.73 1.24 1.36Naphthalene 21.20 0.95 1.042-Methylnaphthalene 19.29 0.87 0.951-Methylnaphthalene 2.71 0.12 0.13DMN 30.60 1.37 1.50TMN 7.89 0.35 0.39
2229.51 100.00 100.00
Selectivities by %C
Results & Discussions
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30
Time on stream [h]
Co
nv
ers
ion
[w
t%] 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
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30
Time on stream [h]
Con
vers
ion
[wt%
]
723 K
673 K
623 K
573 K
The stability of H-ZSM-5 Si/Al =25 on various reaction temperature
TOS <= 17 h stable at ca.100% Conv.
T=673 K
T=723 K T=623 K T=573 K
Results & Discussions
0
20
40
60
80
100
0 5 10 15 20 25 30
Time on stream [h]
Mon
oaro
mat
ic y
ield
[wt%
]723 K
673 K
623 K
573 K
Yield of monoaromatic duing time on stream on various temperature
TOS < 13 h, Yield > 60%
T=723 K
T=673 K
T=623 K T=573 K
Results & Discussions
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 %
Results & Discussions
Si/Al=25, T=673 K
0
20
40
60
80
100
0 10 20 30
Time on stream [h]
Sele
ctiv
ity
[ %
Car
bon]
Si/Al=75, T=673K
0
20
40
60
80
100
0 10 20 30 40
Time on stream [h]
Sele
ctiv
ity
[ %
Car
bon]
Si/Al=100 and T= 673K
0
20
40
60
80
100
0 10 20 30
Time on stream [h]
Sele
ctiv
ity
[ %
Car
bon]
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
Monoiaromatik
C4 Aliphatics
Monoiaromatik
Monoiaromatik
C4 Aliphatics
C4 Aliphatics
Results & Discussions
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
CatalystTotal area,
m2/gMicropore 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
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
CatalystHNZ
5 wt% B2O3-HNZ
15 wt%B2O3-HNZ
25 wt%B2O3-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
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
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]
Ace
ton
e co
nve
rsio
n, %
-1
0
1
2
3
4
5
6
Pa
raff
in/O
lefi
n r
ati
o
Si/Al=25
Paraff in/Olefin
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