Conversion of Poly(Vinyl Chloride) to Fuel Oil Using NiMo Catalyst on Silica Alumina and Acid...

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