conversion of poly(vinyl chloride) to fuel oil using nimo catalyst on silica alumina and acid...
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Conversion of Poly(Vinyl Chloride) to Fuel Conversion of Poly(Vinyl Chloride) to Fuel Oil Using Oil Using
NiMo Catalyst on Silica Alumina and Acid NiMo Catalyst on Silica Alumina and Acid CatalystCatalyst
Dr. Dr. Chanatip S Chanatip Samartamart
Department of Chemistry,Department of Chemistry, ThammasatThammasat University University
Assoc. Prof. Apinya DuangchanAssoc. Prof. Apinya Duangchan
Department of Department of Chemical Engineering Chemical Engineering,, Kasetsart University Kasetsart University
ประชุ�มวิ�ชุาการ วิ�จั ยพลั งงาน สร�างฐานเศรษฐก�จัพอเพ�ยง กร�งเทพฯ 13-14 ธั นวิาคม 2549
IntroductionIntroduction
Plastic polymer Percentage weight
High-density polyethylene (HDPE)Low-density polyethylene (LDPE)Polypropylene (PP)Polystyrene (PS)Polyvinyl chloride (PVC)Polyethylene terephthalate (PET)
31.2531.257.2913.5011.465.21
Table1 Percentage composition of simulated plastic waste.
Recycling TechnologyRecycling Technology
Primary Recycling
Secondary Recycling
Tertiary Recycling
Quaternary Recycling
Tertiary RecyclingTertiary Recycling
Thermal Cracking
Catalytic Cracking
Hydrocracking
Polyvinyl chloride (PVC)Polyvinyl chloride (PVC)
*H
H
*
H
Cln
Fig 1 Structure of polyvinyl chloride
- High mechanical strength- High polar- Non flamable
Polypropylene (PP)Polypropylene (PP)
CH
*
H
H
H H
H
H*n
CH3
3
Fig 2 Structure of polypropylene
- Isotactic- Syndiotactic- Atactic
ExperimentalExperimental
Pyrolysis process diagramPyrolysis process diagramCarrier gas, N2
Plastics
Tube reactor
Cooling water
Liquid product
Gas product
Absorber
Product analysisProduct analysis
- Gas product
Analyzed C1-C3 by gas chromatograph porapak q column equipped with FID detector
- liquid product
Fractionation by distillation in 4 boiling temperature range
IBP-2000C201-2500C251-3700C>3700C
Analysis of gasoline (IBP-200Analysis of gasoline (IBP-20000C) productC) product
- Determination of Benzene Toluene and Xylene (BTX)
Gas chromatograph OV101 column equipped with FID detector
- Determination of Octane Number by NMR
Proton type Chemical shift regionRing aromatic
Olefin-Methyl
Methine (paraffins)Methelene (paraffins)Methyl (paraffins)
6.6 to 8.0 ppm (A)4.5 to 6.0 ppm (B)2.0 to 3.0 ppm (C)1.5 to 2.0 ppm (D)1.0 to 1.5 ppm (E)0.6 to 1.0 ppm (F)
Octane number of gasoline fraction by NMROctane number of gasoline fraction by NMR
A B C D E F
Aromatics, vol % = [(A+C/3) 0.97102] / [(A+C/3)0.97+ 2B+E/2+F/3)1.02+3.33B]
Paraffins, vol% = [(D-2B+E/2+F/3)1.02102] / [(A+C/3)0.97+(D- 2B+E/2+F/3)1.02 +3.33B]
Olefins, vol% = [3.33B102] / [(A+C/3)0.97+(D- 2B+E/2+F/3)1.02+3.33B]
isoparaffin index (CH3:CH2)= 2F:3E
RON = 80.2 + 8.9 (isoparaffin index) + 0.107 (aromatics)
MON = 70.8 + 10 (isoparaffin index) + 0.101 (aromatics)
Result and DiscussionResult and Discussion
Study the decomposition of PVC by TGA Study the decomposition of PVC by TGA
The yields of product at various pyrolysis temperature and carrier gas
0
10
20
30
40
50
60
70
80
90
100
400 500 600 Hydrogen
Temperature (0C)
perce
nt yie
ld %gas
%oil
%solid
Oil and GasTemperature increase to 5000C Solid
At 6000C Gas SolidHydrogen Gas Oil
The gas composition at various pyrolysis temperature and carrier gas
0
0.005
0.01
0.015
0.02
0.025
0.03
400 500 600 Hydrogen
Temperature (0C)
Concentra
tion (m
ol/l)
methane
ethylene
ethane
propane and propylene
Pyrolysis temperature increase Methane yield
0
20
40
60
80
100
400 500 600 Hydrogen,600
Temperature ( 0C)
Perc
ent o
f oil
>370
251-370
201-250
IBP-200
Fraction of liquid products derived from pyrolysis of PVC
Pyrolysis temperature increase Gasoline yield
BTX content of pyrolysed PVC at various temperatures
Temperature BTX content
Hydropyrolysis < PyrolysisBTX content
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
400 500 600 Hydrogen
Temperature (0C)
conc
entra
tion (m
ol/l)
benzene
toluene
xylene
total
-50
-40
-30
-20
-10
0
10
20
30
40
4:1 3:1 2:1 1:1
PP:PVC
%Sy
nerg
ystic
oil
solid
gas
Synergistic effect of PP:PVC for pyrolysis
(oil:gas:solid = 65%:35%:0% for PP and 6.5%:71.3%:22.2% for PVC)
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
1:1 2:1 3:1
PP:PVC
Concentra
tion (m
ol/l)
methane
ethylene
ethane
propane and propylene
The gas composition at various ratio of PP:PVC
At ratio 2:1 and 3:1 give high ethane yield.
Fraction of liquid product derived from different ratios of PP: PVC at 4500C
010
203040
50607080
90100
1:1 2:1 3:1
PP:PVC
Percent o
f produ
ct >370
251-370
201-250
IBP-200
BTX Content in oil from pyrolysis of mixed PP and PVC
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
1:1 2:1 3:1
PP:PVC
Concentra
tion(
mol/l
)
benzene
toluene
xylene
total
The yields of product at various type of catalyst at PP:PVC =1:1
0
10
20
30
40
50
60
70
80
90
100
no catalyst NiMo on alumina silica alumina NiMo on silicaalumina
Type of catalyst
Percent o
f produ
ct
%gas
%oil
%solid
The gas composition at various type of catalyst at PP:PVC = 1:1
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
no catalyst NiMo on alumina silica alumina NiMo on silicaalumina
Type of catalyst
concentra
tion (m
ol/l)
methane
ethylene
ethane
propane and propylene
0
10
20
30
40
50
60
70
80
90
100
no catalyst NiMo on alumina silica alumina NiMo on silica alumina
Type of catalyst
Percent o
f product
>370
251-370
201-250
IBP-200
Fraction of liquid product derived from different type of catalyst at PP:PVC=1:1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
no catalyst NiMo on alumina silica alumina NiMo on silicaalumina
Type of catalyst
concentra
tion (
mol/l
)
benzene
toluene
xylene
total
BTX Content in oil from pyrolysis various type of catalyst at PP:PVC=1:1
Determination of octane numberDetermination of octane number
ชื่��อตั�วอย่�าง PP:PVCอ�ตัราส่�วน ชื่น�ดของตั�วเร�งปฏิ�กิ�ร�ย่า
ปร�มาณตั�วเร�ง (%)ปฏิ�กิ�ร�ย่า
อ�ณหภู�ม�(C)
nmr1 2:1 - - 450nmr2 3:1 - - 450nmr3 1:1 NiMo/Alumina 0.5 450nmr4 1:1 Silica Alumina 0.5 450nmr5 3:1 Silica Alumina 0.5 450
Sample
PP:PVCType of catalyst
% catalyst
Temp
nmr1 4.275818 61.1560335.09887 1.673276 5.92679133.4059130.4998nmr2 3.676634 52.3913843.63832 1.7018735.416191128.7975125.3332nmr3 2.846989 59.4097937.28388 1.66779.436182164.4866165.4494nmr4 2.871626 61.8396334.96509 1.641125 9.80045167.7313169.0945nmr5 4.213647 39.3756155.93149 1.9706864.925741 124.49 120.483
Sample %aromatic %paraffin %olefin H:C isoparafin index RON MON
OO ctane number and hydrocarbon content ctane number and hydrocarbon content
- Low aromatic 2.8-4.3%
- high octane number 120-170
ConclusionConclusionss
Study pyrolysis of PVCStudy pyrolysis of PVC
- When the temperature increases, oil yield increasesWhen the temperature increases, oil yield increases and solid decreases.and solid decreases.- At - At 60060000C solid increases due to polymerization C solid increases due to polymerization reaction.reaction.- Hydrogen decrease the pyrolysis activity- Hydrogen decrease the pyrolysis activity
- At high temperature - At high temperature 60060000C methane is selective inC methane is selective in hydrocarbon gas hydrocarbon gas
- Gasoline decreased but gas oil and residue increase - Gasoline decreased but gas oil and residue increase when temperature was increased due to polymerization when temperature was increased due to polymerization reaction.reaction.
- Benzene Toluene and Xylene (BTX) increased when - Benzene Toluene and Xylene (BTX) increased when temperature was increasedtemperature was increased
- BTX decreased when hydrogen was carrier gas due to - BTX decreased when hydrogen was carrier gas due to BTX was hydrogenated.BTX was hydrogenated.
Study pyrolysis of PVC mix PPStudy pyrolysis of PVC mix PP
- All of ratio have synergistic effect. - All of ratio have synergistic effect.
- Ratio of PP:PVC - Ratio of PP:PVC 2:12:1 and and 3:13:1 showed high yield of showed high yield of hydrocarbon gas. hydrocarbon gas.
- Ethane was selective in hydrocarbon gas.- Ethane was selective in hydrocarbon gas.
- Gasoline and residue yield was high when PP ratio - Gasoline and residue yield was high when PP ratio increased.increased.
- BTX decreased at high PP ratio because alkylation - BTX decreased at high PP ratio because alkylation reaction generated reaction generated to isoparaffinto isoparaffin..
Study effect of catalystStudy effect of catalyst
- NiMo/Al2O3 catalyzed hydrogenation dehydrogenation - NiMo/Al2O3 catalyzed hydrogenation dehydrogenation reaction.reaction.
- Silica alumina catalyzed cracking reaction- Silica alumina catalyzed cracking reaction
- NiMo/SiO2Al2O3 was bifunctional catalyst and catalyzed - NiMo/SiO2Al2O3 was bifunctional catalyst and catalyzed dehydrocyclization.dehydrocyclization.
AcknowledgementsAcknowledgements
- Department of Chemistry, Kasetsart University
- Department of Chemistry, King Mongkut Institute of Technology Ladkrabang
- Ministry of Energy (EPPO)
- Department of Chemical Engineering, Kasetsart University
- The university staff development project of commission on higher education scholarship