LDPE

LDPE
Technology
Technology
2010
2010
El
El

ad
ad

: Csernyik Istv
: Csernyik Istv

n
n
2 2
Content
Content

What is LDPE
What is LDPE

Application
Application

History
History

Process theory
Process theory

Autoclave process
Autoclave process

Tubular process
Tubular process

Process steps
Process steps

Process control
Process control

Process safety
Process safety

Key equipment
Key equipment

Investment cost
Investment cost

Cost of production
Cost of production
3 3
What is LDPE
What is LDPE

L
L
ow
ow
D
D
ensity
ensity
P
P
oly
oly
E
E
thylene
thylene

Typical properties
Typical properties

Density
Density
0,91
0,91
5
5
-
-
0,93
0,93
5
5

Melt index
Melt index
0,3
0,3
-
-
>
>
20 g/10 min (190 C/2,16
20 g/10 min (190 C/2,16
kg)
kg)

Melting point
Melting point
120 C
120 C

Polydispersity
Polydispersity
5,5
5,5

6 (TVK tubular
6 (TVK tubular
g
g
rades
rades
)
)
4 4
Application
Application
Film
65%
Extrusion
coating
10%
Other
14%
Injection
moulding
7%
Blow
moulding
4%
5 5
Application by Properties
Application by Properties
0,1
1
10
100
0,915 0,92 0,925 0,93 0,935
EXTRUSION COATING
FILM EXTRUSION
INJECTION MOULDING
EXTRUSION COATING
BLOW MOULDING
M
I
,

g
/
1
0

m
i
n
/
1
9
0

C
Density, kg/dm
3
6 6
History
History

LDPE was discovered by ICI in 1933
LDPE was discovered by ICI in 1933

autoclave
autoclave
process
process
in
in
1938
1938

BASF developed the first tubular process during WW II
BASF developed the first tubular process during WW II

High variation of autoclave and tubular processes by
High variation of autoclave and tubular processes by
different licensors
different licensors

Nowadays licences available up to 400
Nowadays licences available up to 400
kt/y
kt/y
plant
plant
capacity
capacity

Global consumption
Global consumption
in
in
2009:
2009:
1
1
8
8
million
million
t
t

TVK LDPE plants
TVK LDPE plants
1970 1970 - - ICI autoclave process 24 ICI autoclave process 24 kt/y kt/y debottlenecked debottlenecked to 50 to 50 kt/y kt/y
1991 1991 - - BASF tubular process 60 BASF tubular process 60 kt/y kt/y
7 7
Process Theory
Process Theory
1
1

Free radical reaction
Free radical reaction

I nitiation
I nitiation
I I

R R

+ R + R
Initiators: typically organic Initiators: typically organic

peroxides peroxides

Propagation
Propagation
R R

+ CH + CH

2 2

CH CH

2 2
RCH RCH

2 2

CH CH

2 2


R(CH R(CH

2 2

CH CH

2 2

) )

n n- -1 1

CH CH

2 2

CH CH

2 2



+ +

CH CH

2 2

CH CH

2 2


R(CH R(CH

2 2

CH CH

2 2

) )

n n

CH CH

2 2

CH CH

2 2



Termination
Termination
Combination Combination
R R

x x



+ +

R R

y y



P P

x x+y +y
Disproportion Disproportioning ing
R R

x x



+ +

R R

y y



P P

x x
+ + P P

y y
8 8
Process Theory
Process Theory
2
2

Other reactions
Other reactions

Chain transfer
Chain transfer

important to control
important to control
molecular weight
molecular weight
R
R
x x

+ CH
+ CH
2 2

CH
CH
2 2

P
P
x x
+ R
+ R
1 1

by monomer
by monomer
R
R
x x

+
+
M
M

P
P
x x

+ M
+ M

by modifier
by modifier

Cracking
Cracking

results in shorter chains

results in shorter chains
R
R
x x

P
P
y y

+ R
+ R
x x- -y y

9 9
Process Theory
Process Theory
3
3
Branching
Branching

LDPE characterised by high degree
LDPE characterised by high degree
of short and long chain branching
of short and long chain branching
Short chain branching Short chain branching responsible for density responsible for density
Intramolecular Intramolecular

chain transfer and copolymerisation result in chain transfer and copolymerisation result in
short chain branches short chain branches
Long chain branching Long chain branching
Intermolecular chain transfers give long chain branches Intermolecular chain transfers give long chain branches
C
C
H
C C
C
C C C C
C C C
H
C C C
C C C
10 10
LDPE
LDPE
-
-
Autoclave Process
Autoclave Process
Initiators
(Peroxides)
Autoclave
reactor
Secondary
compressor
Primary
compressor
280 bar
250 C
HP separator
Wax
separator
0,5 bar
250 C

LP separator
Extruder
Ethylene
Oil
separator
250 bar
1400 bar
170 C
240 C
280 C
Bagging
Bulk loading
Degassing
11 11
Autoclave
Autoclave
Reactor
Reactor
Autoclave reactor MK 10
L = 4750 mm d = 18
Thermocouple 1
(1st T control)
Thermocouple 2
Thermocouple 4
(2nd T control)
Thermocouple 5
Thermocouple 6
Thermocouple 7
(control 2nd zone T)
Thermocouple 8
Thermocouple 9
(control 3rd zone T)
Thermocouple 10
(control 4th zone T)
Thermocouple 3
Top Zone
2
nd
Zone
3
rd
Zone
4
th
Zone
Total 725 l
ethylene
peroxides
12 12
LDPE
LDPE
-
-
Tubular Process
Tubular Process
Modifier
Fresh Ethylene
Purge
Initiator
(Oxygen)
Primary
Compressor
Secondary
Compressor
Preheater
Precooler
Reaction
Zone I
Reaction
Zone II
HP Separator
LP Separator
Extruder
HP Recycle
LP Recycle
280 bar
250 C
0,5 bar
250 C
2400-2900 bar
180-310 C
250 bar
Bagging
Bulk loading
Degassing
13 13
Autoclave vs. Tubular Process
Autoclave vs. Tubular Process
Autoclave Autoclave
Conversion up to 21% Conversion up to 21% - -
adiabatic, reaction heat adiabatic, reaction heat
removed by reactant only removed by reactant only
1300 1300- -2000 bar operating 2000 bar operating
pressure pressure
Higher capacity of hyper Higher capacity of hyper
compressor compressor
Organic peroxide initiators only Organic peroxide initiators only
Specialty polymer capability Specialty polymer capability
EVA copolymers over 40% EVA copolymers over 40%
vinyl acetate vinyl acetate
Lower reactor capacity Lower reactor capacity 150 150
kt/y kt/y
Tubular Tubular
Conversion up to 36% Conversion up to 36% - -
r rea eaction ction heat partly removed heat partly removed
by coolant by coolant
2500 2500- -3200 bar operating 3200 bar operating
pressure pressure
Lower capacity of hyper but Lower capacity of hyper but
higher load higher load
Cheaper oxygen initiator Cheaper oxygen initiator
possible possible
Film Film grades with higher clarity grades with higher clarity, ,
EVA up to 10% vinyl acetate EVA up to 10% vinyl acetate
Reactor capacity up to 400 Reactor capacity up to 400
kt/y kt/y
14 14
Process Steps 1
Process Steps 1

Compression
Compression
Increase make up ethylene Increase make up ethylene
pressure to reaction pressure to reaction
pressure pressure
Recycle Recycle unreacted unreacted ethylene ethylene
Inject modifier and Inject modifier and
comonomer comonomer

Reaction
Reaction
Injection of initiators Injection of initiators
Control temperatures for Control temperatures for
required product properties required product properties
One phase reaction One phase reaction two two
phase only at lower phase only at lower
pressure and temperature pressure and temperature
Short residence time Short residence time
some minutes some minutes
15 15
Process Steps 2
Process Steps 2
HP separator HP separator
Separate melt LDPE and Separate melt LDPE and
unreacted unreacted ethylene ethylene
LP separator LP separator
Remove Remove unreacted unreacted ethylene ethylene
Feed tank for extruder Feed tank for extruder
HP recycle HP recycle
Remove low molecular weight Remove low molecular weight
polymer (wax) polymer (wax)
Cool down recycle ethylene Cool down recycle ethylene
LP recycle LP recycle
Remove low molecular weight Remove low molecular weight
polymer (wax, oils) polymer (wax, oils)
Cool down recycle ethylene Cool down recycle ethylene
16 16
Process Steps 3
Process Steps 3

Extrusion
Extrusion

Homogenization
Homogenization

Additive dosing
Additive dosing

Pelletizing
Pelletizing

Degassing
Degassing

Remove residual
Remove residual
ethylene (generally
ethylene (generally
less than 1000
less than 1000
ppm
ppm
)
)
from LDPE
from LDPE

to avoid
to avoid
explosive gas mixtures
explosive gas mixtures
17 17

Melt index (Molecular weight)
Melt index (Molecular weight)

P
P

MI
MI

(M
(M
w w

)
)

T
T

MI
MI

(M
(M
w w

)
)

[Modifier]
[Modifier]

MI
MI

(M
(M
w w

)
)

Density
Density

P
P

D
D

T
T

D
D

Pressure range: 1300
Pressure range: 1300
-
-
3000 bar
3000 bar

Temperature range: 160
Temperature range: 160
-
-
310 C
310 C
Process Control
Process Control
18 18

Risk of decomposition
Risk of decomposition
Decomposition: ethylene or polyethylene Decomposition: ethylene or polyethylene decomps decomps to C and H to C and H
2 2
High temperature, high pressure, contaminations favour High temperature, high pressure, contaminations favour
decomposition decomposition

Reactor and HP separator in confined area
Reactor and HP separator in confined area

generally
generally
behind concrete wall
behind concrete wall

Interlock system to
Interlock system to
avoid decomposition and avoid decomposition and
protect equipment protect equipment

Special metal gaskets at high pressures
Special metal gaskets at high pressures

Gas detectors
Gas detectors

Fire fighting system
Fire fighting system
Process Safety
Process Safety
19 19
Key Equipment
Key Equipment

Compressors
Compressors

Primary compressor (
Primary compressor (
Booster+Primary
Booster+Primary
)
)

5 stages
5 stages

0,1 bar suction; 250 bar discharge
0,1 bar suction; 250 bar discharge

Secondary compressor (Hyper)
Secondary compressor (Hyper)

Two stages
Two stages

250 bar suction; 3000 bar discharge
250 bar suction; 3000 bar discharge

Extruder
Extruder

Hot melt extruder for homogenization
Hot melt extruder for homogenization
20 20
Hyper
Hyper
Compressor
Compressor
Arrangement
Arrangement
21 21
Hyper
Hyper
Compressor
Compressor
Cylinder
Cylinder
22 22
Extruder
Extruder
Arrangement
Arrangement
23 23
Single
Single
-
-
screw
screw
Extruder
Extruder
24 24
Investment cost
Investment cost
Basis: USGC 2008Q1
Basis: USGC 2008Q1
Process Autoclave Autoclave Tubular
Plant size 135 kt 3x135 kt 400 kt
ISBL 91,7 231,6 130,1
OSBL 60,6 142,3 118,4
Other project cost 61,2 160,5 125,1
Total investment 213,5 534,4 373,6
Specific investment,
USD/t
1581 1320 934
million USD
25 25
Cost of Production
Cost of Production
Basis: USGC 2008Q1
Basis: USGC 2008Q1
Autoclave Autoclave Tubular
135 kt 3x135 kt 400 kt
USD/t
Ethylene 1354 1354 1347
Catalysts&chemicals 8 8 5
Additives 14 14 14
Total raw materials 1376 1376 1366
Power 51 51 58
Other utilities 9 9 7
Steam credit -34
Total utilities 60 60 31
Direct cash cost 34 22 14
Allocated cash cost 37 27 18
Total fixed costs 71 49 32
Total cash cost 1507 1485 1429
80%
85%
90%
95%
100%
135 kt 3x135 kt 400 kt
Autoclave Autoclave Tubular
Tot al f ixed cost s
Tot al ut ilit ies
Tot al r aw mat er ials
26 26
Appendix: Metal Gasket
Appendix: Metal Gasket
27 27
Appendix: Hyper compressor cylinder
Appendix: Hyper compressor cylinder
28 28
Appendix:
Appendix:
Blown Film Extrusion
Blown Film Extrusion
29 29
Appendix:
Appendix:
Extrusion Coating
Extrusion Coating