A Green Chemistry Module

Petretec – Dupont’s Technology for

Polyester Regeneration

Presidential Green Chemistry Challenge Award

World Proven Reserves of Crude Oil

20.6 65.4
63.7 44.0
675.7
74.9
89.5

thousand million barrels

World Proven Crude Oil Reserves

as percent of 1296 thousand million barrel total

 Composition of Crude Oil

CRUDE OIL

HYDROCARBONS NON-HYDROCARBONS

ALIPHATICS AROMATICS NAPHTHENES SULFURS NITROGENS OXYGENS METALLICS

25% 17% 50% <8% <1% <3% <100PPM

C1 - C60 (C6H5)n O
CYCLOALKANES
SH

N
H
COOH
S
 Crude Oil Classification

PETROLEUM
Saturates Asphaltics
n-alkanes C5 - C44 nitrogen
branched alkanes
Aromatics oxygen containing compounds
cycloalkanes (napthenes) single ring sulfur
condensed ring

API Gravity = 35o

The Uses of Crude Oil
 The Xylenes

CH 3 CH3 CH 3
CH 3

CH3
CH 3
ortho meta para
Boiling Point 144oC 139.3oC 137-138oC
Melting Point -25oC -47.4oC 13-14oC
CRUDE Petroleum delivered from well field

DESALTING Water washing to remove impurities

REFINING
Distillation to separate by boiling point
ranges

REFORMING Conversion reactions to alter

molecular structures

Mixing to obtain maximum commercial

BLENDING
characteristics
 Petroleum Refining
C1-C4
GAS bp < 50 oF

T LIGHT NAPHTHA
C5 - C?
bp 50-200oF

O HEAVY NAPHTHA
C? - C12
bp 200-400oF
W
C12 - C16
E KEROSENE
bp 400-500oF
CRUDE DESALTER FURNACE
R ATM. GAS OIL C15 - C18
bp 500-650oC

> C20
RESIDUUM
bp >650oF

Distillation – separation by boiling point

 Petroleum Reforming
GAS FUEL GAS

T LIGHT NAPHTHA TREATER

O HEAVY NAPHTHA HYDROTREATER REFORMER AROMATIC

GASOLINE

W EXTRACTION
AROMATICS
E KEROSENE HYDROTREATER
JET FUELS/KEROSENE

R ATM. GAS OIL HYDROTREATER CATALYTIC

CRACKER DIESEL & FUEL OILS

RESIDUUM
CATALYTIC
VACUUM GAS OIL CRACKER
Vacuum LUBRICATING OIL
Distillation
ASPHALT

COKER COKE
Conversion Reactions
THERMAL
C7H15.C15H30.C 7H15 C7H16 + C 7H14 + C15H30
CRACK gasoline gasoline additive recycle

CATALYTIC

ALKYLATION CH3 CH2CH3 CH2 CH CH2 CH3 CH3CH2CH2 CH2 CH2CH2CH3

COMBINE
18% 82%

POLYMERIZATION
CH3 H CH3
CH3
C CH C H3C CH2 C CH2 C H3C CH2 C CH2 H3C C H3C
CH3 CH3
CH3 CH3 CH3 CH3

REFORMIING Dehydrogenation
Dehydroisomerization
REARRANGE
Isomerization
ISOMERIZATION Dehydrocyclization
Hydrocracking
Catalytic Reforming – Conversion Reactions
Dehydrogenation of cycloalkanes to aromatics

CH3 CH3

3H2

Dehydroisomerization of cyclopentanes to aromatics

CH3

3H2

Isomerization of alkanes

CH3
CH3CH2CH2CH2CH3 H3C CH CH2 CH3

Dehdrocyclization of alkanes
CH3

CH3CH2CH2CH2CH2CH2CH3 4 H2

Hydrocracking of alkanes

CH3CH2CH2CH2CH2CH2CH3 CH3CH2CH3 CH3CH2CH2CH3

 Preparation of PET monomers
Formation of ethylene glycol
OH OH
O2 O
H2C CH 2 H 3C CH CH CH 3
Ag

Formation of TA and DMT

O OH
C H3 C

[ O2 ]

C H3 C
C H OH O OH
C H 3 OH / C o O2 3
TA
O OC H3
C

C
O OC H3

D MT
 PET Polymerization Reactions
Step Growth Polymerization - Condensation O O
O O high Temp
n C C n HO CH2 CH2 OH C C O CH2 CH2 O
-H2O
HO OH n

Ester Interchange - Transesterification

O O
n CH3O C C OCH3 2n HO CH2 CH2 OH

low Temp - 2n CH3OH

O O
HO CH2 CH2 O C C O CH2 CH2 OH

O O
C C O CH2 CH2 O
n
 SCRAP PET

The Dupont Contaminated PET PET for Recycling

DMT
o
Temp > 220 C

Landfill/Incinerate Mechanical

Petretec Recycling PET / DMT

solution

Process METHANOLYSIS REACTOR

o
CH3OH, 260-300 C, 340-650kPa

For DMT + Ethylene Glycol

excess CH3OH

Methanol removal column

Polyester CH 3OH DMT / Ethylene Glycol

azeotrope
MPT
distillation

Regeneration MPT / Ethylene Glycol DMT

Ethylene Glycol / MPT

distillation
Pure DMT
 Petretec Polyester Regeneration

Methanolysis Reactor

O O O O
CH3OH
C C O CH2 CH2 O n C C n HO CH2 CH2 OH
CH3O OCH3
n

260-300oC 340-650 kPa