Dr. N. Lingaiah Senior Scientist

Catalysis Laboratory, I&PC Division

Indian Institute of Chemical Technology,

Hyderabad

Conversion of Waste Plastics into Fuel Oil

using Solid Acid Catalyst

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

Plastics - The problems

Sector wise Waste Plastic Generation

Packaging materials : 42%

Consumer Products : 25%

Building & construction : 14%

Industrial Goods : 13%

Mixed Plastic : 6%

Waste Plastics: Indian Scenario

+

Residue

(carbon)

+

Lighter hydrocarbons

Used to heat the reactor

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

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

M/s Haritha-NTI Ltd evaluated IICT catalysts and compared with

the commercial catalysts procured from abroad.

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 1 538 15 470 0.74 70

500 0.2 535 12 450 0.73 80

500 0.5 530 18 500 0.74 80

500 1 535 17 500 0.68 82

HNTI Catalyst

IPC-IICT Catalyst

Technology Transfer

500 kg catalyst was prepared in IICT and provided to Haritha-NTI for commercial operation.

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

Glyceric acid;

glyceraldehyde etc

Acrolein &

acetol

Propane diols

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

HO

OH

O

OH

OH

O

OHHO

O

OHHO

OH

OHO

HO

OH

HO OH

O

O O

O

OH

O

OO

Oxidation Ca

rbo

xyla

tio

n

Mono, di & Triacetin

Glycerol

carbonates

9

Glycerol hydrogenolysis

Lower metal containing catalyst is developed for selective

hydrogenolysis of glycerol.

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

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

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

Cu based catalysts for glycerol hydrogenolysis

Catalyst Conv. (%)

Selectivity (%)

1,2PDO EG

10CuMgO 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

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

11

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

HYDROGENOLYSIS USING

CRUDE AND SULFATE CONTAINING GLYCEROL

The catalyst showed better tolerance towards salts and other

impurities present in crude glycerol.

12

UP SCALING STUDIES

glycerol conversion is marginally varied during up scaling of the

reaction

Vol.

(ml)

Conv.

(%)

Selectivity (%)

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

13 The catalyst showed good recyclability. The catalysts is exhibiting

similar conversion and selectivity up in reusing.

Recycle Experiments

10 20 30 40 50 60 70 80

Used

Fresh

In

tensi

ty (

a.u

.)

2 Theta

Thank You

ధన్యవాదాలు

Acknowledgements

The Director, IICT

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

16

(a)

(b)

(c)

Proton sites in heteropoly acids :

(a) HPA in solution (b) solid PW hexahydrate (c) solid dehydrated PW

Where is the proton ?

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

Proton location

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

(a)

(b) (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

Heteropoly acid (HPA)

Calcination

Support

Catalyst

Aqueous HPA Solution

Evaporation of

excess water

H2O

Preparation of Supported HPAs

Precursor of

HPA

In-situ generation of

HPA

Support

Solvent evaporation

Calcination

Catalyst

Preparation of Supported modified HPAs

OH

Sn 1

H[P

W 12O 40

]

HSn1 [P

W12 O

40 ]

O

H

Sn1H[PW12O40]

O

H

H

H2O

OH

H

R2

Sn1H[PW12O40]

Sn1[PW12O40]

[PW12O40]Sn1H

Path

I

Path

II

R1

R1 R1

R1

R2

R2 R2

R2

Lew

isAcid

Bro

nsted

Acid