Conversion of Waste Plastics into Fuel Oil

using Solid Acid Catalyst

Dr. N. Lingaiah
Senior Scientist
Catalysis Laboratory, I&PC Division
Indian Institute of Chemical Technology,
Hyderabad

Plastics - The problems

Plastics
Are not degradable - It takes
years to degrade
Contribute to global emissions
(Methane)
Harmful to health and
environment

Disposal ?
Release toxic gases when burnt
Plastics contribute 28 percent in
municipal solid waste

Sector wise Waste Plastic Generation

Packaging materials

: 42%

Consumer Products

: 25%

Building & construction : 14%

Industrial Goods

: 13%

Mixed Plastic

: 6%

Waste Plastics: Indian Scenario

Solution- Polymer Energy

Catalytic approach for the conversion of waste plastics: Waste not & want not
This technology is an environment friendly, economically viable solution.

Project Sponsored by
Harita NTI ( a TVS associate )
sponsored the project for the
development of indigenous catalyst
Budget

: 10.5 Lakhs for initial studies

25 lakhs for technology transfer
Duration : 9 months

+ Residue
(carbon)

+
Lighter hydrocarbons
Used to heat the reactor

Preparation of IPC-IICT catalyst for waste plastic recycling

IICT developed a solid acid based catalyst for the

degradation of waste plastics

Important aspects of the catalyst:

Preparation of catalysts is simple
Only two unit operations are involved

The cost of the catalyst is cheap

Easy to scale up

Reproducible

Waste plastic recycling reactors located at Harita-NTI plant

in Ambattur Industrial Estate,Chennai

Technology Transfer
M/s Haritha-NTI Ltd evaluated IICT catalysts and compared with
the commercial catalysts procured from abroad.

HNTI Catalyst

IPC-IICT Catalyst

Quantity
of Plastic
(g)

Catalyst
amount
(%)

Reaction
Temperature
(C)

Total
output
time
(min)

Quantity
of oil
(ml)

Densit
y of oil
(g/ml)

Efficiency
of the
system (%)

500

0.2

534

19

440

0.80

70

500

0.5

531

13

450

0.76

68

500

538

15

470

0.74

70

500

0.2

535

12

450

0.73

80

500

0.5

530

18

500

0.74

80

500

535

17

500

0.68

82

Catalyst preparation was demonstrated at a scale of 15 Kg for batch

500 kg catalyst was prepared in IICT and provided to

Haritha-NTI for commercial operation.

Value-added Molecules from Biodiesel By-product: The Glycerol Challenge

O

Glycerol
carbonates
O

OH

HO
O
HO

OH
OH

HO

OH

Oxidation

OH

Carboxylation

OH

OH
HO

OH
HO

Propane diols

HO

Glyceric acid;
glyceraldehyde etc

O
OH
O

O
O

Mono, di & Triacetin

Acrolein &
acetol

Glycerol hydrogenolysis
Catalyst

Conv.
(%)

Selectivity (%)
2PO

1PO Acetol 1,2PD

EG

1,3PD

Others

Cat-1

36

8.5

4.5

0.2

58.9

22.5

1.2

4.2

Cat-2

45.8

8.2

5.1

0.1

62.6

19.5

1.5

2.7

Cat-5

44.8

7.2

5.6

6.1

57.7

16.9

1.0

3.8

Cat-7

40.4

6.9

1.9

5.6

64.2

17.8

0.3

1.3

Reaction Conditions: Temperature: 180 C; H2 Pressure: 60 bar; Glycerol

Conc.: 20wt%; Reaction time: 8 h

Lower metal containing catalyst is developed for selective

hydrogenolysis of glycerol.
9

Cu based catalysts for glycerol hydrogenolysis

Catalyst

Conv. (%)

Selectivity (%)
1,2PDO

EG

30.2

91.8

5.4

20CuMgO

49.3

92.3

5.9

40CuMgO

36.6

90.3

6.7

60CuMgO

18.0

90.0

6.9

80CuMgO

6.1

87.6

5.6

10CuMgO

Reaction Conditions: Glycerol Conc.: 20wt%; H2 Pressure: 40 bar, Reaction time:

8h, Catalyst Wt: 6%

N. Lingaiah et al. Catalysis Science & Technology, 2 (9) (2012) 1967 - 1976

HYDROGENOLYSIS USING
CRUDE AND SULFATE CONTAINING GLYCEROL
Type of glycerol

Conv.
(%)

Selectivity (%)
1,2-PD

EG

1,3-PD

Others

Glycerol LR (99%)

45.8

62.9

19.5

1.5

16.1

Glycerol - +5% Na2SO4

41.8

58.9

21.7

1.2

18.2

Type of glycerol

Conv.
(%)

Selectivity (%)

1,2-PD

EG

1,3-PD

Others

Glycerol - LR (99%)

45.8

62.9

19.5

1.5

16.1

Crude glycerol

42

59

20.4

0.7

19.9

The catalyst showed better tolerance towards salts and other

impurities present in crude glycerol.
11

UP SCALING STUDIES

Vol.
(ml)

Conv.
(%)

2-PO

1-PO

Acetol

1,2-PD

EG

1,3-PD

Others

50

45.8

8.2

5.1

0.1

62.9

19.5

1.5

2.7

200

46.2

9.6

6.3

0.7

55.5

23.0

1.1

4.9

500

40.1

8.2

4.9

0.2

55.7

28.2

1.0

1.8

Selectivity (%)

glycerol conversion is marginally varied during up scaling of the

reaction

12

Intensity (a.u.)

Recycle Experiments

Used

Fresh
10

20

30

40

50

60

70

80

2 Theta

The catalyst showed good recyclability. The catalysts is exhibiting

similar conversion and selectivity up in reusing.

13

Thank You

Acknowledgements
Dr. P. S. Sai Prasad
Dr. K. S. Rama Rao
Dr. R. B. N. Prasad
Research Scholars
Dr. K.N. Rao
Dr. N. Seshu Babu
Mr. K. T. Venkateswara Rao
Mr. P. S. N. Rao
Mr. Ch. Ramesh Kumar
Mr. K. Jagadeesh
Ms. A. Srivani
Ms. V. Rekha
Mr. Hari Babu
Mr. Srinivas
All the colleagues of I&PC Division

The Director, IICT

Dr. M. Lakshmi Kantam, Head, I&PC Division

Where is the proton ?

(a)

(b)

(c)
Proton sites in heteropoly acids :
(a) HPA in solution (b) solid PW hexahydrate (c) solid dehydrated PW
Ivan V. Kozhevnikov, Catal. Rev. Sci. Eng. 37(2), 1995, 311

16

Proton location
Proton sites in heteropoly acids :
(a) HPA in solution (b) solid PW
hexahydrate (c) solid dehydrated PW

(a)

(b)

Ivan V. Kozhevnikov, Catal. Rev. Sci. Eng. 37(2), 1995, 311

(c)

Supported HPAs
HPA can be supported on acidic and neutral supports
Carbon, Silica, Titania, Zirconia, Niobia,Zeolites

Problems associated with the preparation of supported modified HPAs

Most of metal exchanged/incorporated or salts of HPAs are not soluble in aqueous
media
Preparation of Supported HPAs

Preparation of Supported modified HPAs

Precursor of
HPA

Heteropoly acid (HPA)

H 2O
Aqueous HPA Solution

In-situ generation of
HPA

Support

Support

Evaporation of
excess water

Solvent evaporation

Calcination
Catalyst

Calcination

Catalyst

R1

O
H

40

ci
d

12

Sn1H[PW 12O40]

Le
w
is

Sn

Pa
th
I
[P
W

R2

Sn 1H[PW12 O40]

OH
H

R2

OH

R1

R1
R

R2

H
H 2O

II

12

Sn1 [PW12O 40]

40

d
te
ns

W
[P

o
Br

th
Pa

Sn
H

R1

id
Ac

R2

O
H

[PW 12O40]Sn1