HDPE Technology

HDPE Technology
Including MDPE and LLDPE
Including MDPE and LLDPE
2010
2010
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El

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ad

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Content
Content

HDPE, MDPE and LLDPE
HDPE, MDPE and LLDPE

linear
linear
polyethylenes
polyethylenes

Application
Application

History
History

Catalysts
Catalysts

HDPE processes
HDPE processes

Process control
Process control

Process safety
Process safety

Key equipment
Key equipment

Investment cost
Investment cost

Cost of production
Cost of production
3 3
The Linear Polyethylene Family
The Linear Polyethylene Family
HDPE, MDPE, LLDPE HDPE, MDPE, LLDPE: : linear polyethylenes linear polyethylenes
Classification by density Classification by density determined by short chain branching determined by short chain branching through through
comonomer content comonomer content
Properties Properties
Melt index Melt index 0,03 0,03 - - >100 g/10 min (190 C/2,16 kg) >100 g/10 min (190 C/2,16 kg)
Melting point Melting point 120 120- -140 C 140 C
Polydispersity Polydispersity (TVK (TVK grades grades) )
Monomodal Monomodal 6 6- -8 8
Bimodal Bimodal 10 10- -20 20
0,915 0,926
0,940 0,970
No of SCB
LLDPE
MDPE
HDPE
4 4
Application
Application

HDPE/MDPE
HDPE/MDPE

LLDPE
LLDPE
Fi l m
77%
Extrusi on
coati ng
6%
Inj ecti on
moul di ng
5%
Other
12%
Film
16%
Fiber
2%
Blow
moulding
36%
Injection
moulding
20%
Pipe
22%
Other
4%
5 5
Application by
Application by
Properties
Properties
0,01
0,1
1
10
100
0,890 0,900 0,910 0,920 0,930 0,940 0,950 0,960 0,970
Narrow MWD
Medium MWD
Broad MWD
LLDPE
INJECTION
MOULDING
LLDPE
BLOWN & CAST
FILM
MDPE
YARN
FILAMENTS
HDPE
BLOW MOULDING
HDPE
FILM
PIPES
HDPE
INJECTION
MOULDING
M
F
R

(
g
/
1
0

m
i
n
M
F
R

(
g
/
1
0

m
i
n
) )
Density Density (g/cc) (g/cc)
LLDPE-MDPE-HDPE
WIRE AND CABLE
(Medium to broad MWD)
MDPE
ROTOMOULDING
6 6
History
History

HDPE discovered in 1951 by P. Hogan and R. Banks
HDPE discovered in 1951 by P. Hogan and R. Banks

Mid 1950s: commercial HDPE production in slurry process
Mid 1950s: commercial HDPE production in slurry process
(Hoechst) and solution process (Phillips Petroleum)
(Hoechst) and solution process (Phillips Petroleum)

1961: slurry loop reactor technology by Phillips Petroleum
1961: slurry loop reactor technology by Phillips Petroleum

1968: first gas phase process by Union Carbide
1968: first gas phase process by Union Carbide

Mid 1970s: first LLDPE process by Union Carbide
Mid 1970s: first LLDPE process by Union Carbide

Various processes available up to 400 kt/y capacity
Various processes available up to 400 kt/y capacity

Global consumption
Global consumption
, 2009
, 2009
HDPE/MDPE HDPE/MDPE 30 million t/y 30 million t/y
LLDPE LLDPE 19 19,2 ,2 mi mil llion t/y lion t/y

TVK HDPE plants
TVK HDPE plants
1986: Phillips slurry loop process 140 kt/y, debottlenecked to 1 1986: Phillips slurry loop process 140 kt/y, debottlenecked to 190 kt/y 90 kt/y
2004: Mitsui slurry, cascade reactor technology 200 kt/y 2004: Mitsui slurry, cascade reactor technology 200 kt/y
7 7
Catalysts
Catalysts

Chromium
Chromium
Silica supported hexavalent Cr Silica supported hexavalent Cr
Activation at high temperature before use Activation at high temperature before use
Cocatalyst not necessary Cocatalyst not necessary
Medium to broad molecular weight distribution Medium to broad molecular weight distribution

Ziegler(
Ziegler(
-
-
Natta)
Natta)
MgCl MgCl
2 2
supported TiCl supported TiCl
4 4
Metal alkyl cocatalyst necessary Metal alkyl cocatalyst necessary
Narrow molecular weight distribution Narrow molecular weight distribution
Preferred for bimodal products in cascade reactor technology Preferred for bimodal products in cascade reactor technology
very broad MWD very broad MWD

Metallocene (single site)
Metallocene (single site)
Still developing Still developing
Cocatalyst necessary Cocatalyst necessary
Very narrow molecular weight distribution Very narrow molecular weight distribution
Bimodal capability in single reactor technology Bimodal capability in single reactor technology
8 8
Processes and Products
Processes and Products
Gas phase
Gas phase
processes
processes
Solution
Solution
processes
processes
Slurry
Slurry
processes
processes
H
D
P
E
/
M
D
P
E
L
L
D
P
E
Loop slurry only
High quality film grades
Best for blow moulding
and pipe grades
Melt index limit
with density limit
9 9
Gas Phase Process
Gas Phase Process
Polymerization
Polymerization
Gas phase process
85-110 C
20-25 bar
10 10
Gas Phase Process
Gas Phase Process
Additivation and Pelletizing
Additivation and Pelletizing
11 11
Gas
Gas
Phase
Phase
Processes
Processes
Characteristics
Characteristics

Catalyst
Catalyst
:
:
chromium
chromium
,
,
Ziegler
Ziegler
, (
, (
metallocene
metallocene
)
)

Fluidized
Fluidized
bed
bed
reactor
reactor

70
70
-
-
110 C
110 C

15
15
-
-
30 bar
30 bar

Long
Long
residence
residence
time
time

Swing
Swing
technology
technology
: LLDPE
: LLDPE

HDPE
HDPE
capability
capability

Simple
Simple
process
process
design
design

Low
Low
investment
investment
and
and
operating
operating
cost
cost

Bimodal
Bimodal
capability
capability
with
with
two
two
reactors
reactors
12 12
Solution Process
Solution Process
150-250 C
30-100 bar
13 13
Solution Process
Solution Process
es
es
Characteristics
Characteristics

Catalyst
Catalyst
:
:
Ziegler
Ziegler
, (
, (
metallocene
metallocene
)
)

Polymerisation
Polymerisation
takes
takes
place
place
in
in
solution
solution

30
30
-
-
130 bar
130 bar

150
150
-
-
300 C
300 C

Short
Short
residence
residence
time
time

Broad
Broad
product
product
range
range
: LLDPE
: LLDPE

HDPE
HDPE

Bimodal
Bimodal
capability
capability
with
with
cascade
cascade
reactors
reactors

Higher
Higher
investment
investment
and
and
operating
operating
cost
cost
14 14
Chevron
Chevron
Phillips Slurry Loop Process
Phillips Slurry Loop Process
15 15
Chevron
Chevron
Phillips Slurry Loop Process
Phillips Slurry Loop Process
Characteristics
Characteristics

Catalyst
Catalyst
:
:
chromium
chromium
,
,
Ziegler
Ziegler
, (
, (
metallocene
metallocene
)
)

Chromium catalyst activation
Chromium catalyst activation
Fluidized bed activator Fluidized bed activator
Heat treatment in air at 600 Heat treatment in air at 600- -870 C 870 C

Reaction in loop reactor
Reaction in loop reactor
85 85- -105 C; 42 bar 105 C; 42 bar
3 3- -6 % ethylene concentration 6 % ethylene concentration
Isobutane diluent Isobutane diluent
Heat removed by coolant Heat removed by coolant in in reactor jacket reactor jacket very good very good
surface/volume ratio surface/volume ratio

Flash separation
Flash separation
10 bar; 80 C 10 bar; 80 C

Degassing
Degassing
85 C; 0,1 bar 85 C; 0,1 bar
16 16
Phillips
Phillips
Process
Process
at
at
TVK
TVK
Polymerisation
Polymerisation
Circulating
Pump
Hexene-1
Comonomer
Ethylene
C
a
t
a
l
y
s
t
Hexene-1
Purification
Ethylene
Purification
Isobutane Distillation
and Purification
Ethylene
Compressor
Flash Gas
Compressor
Flash Gas
Filter
Flash
Tank
Dryer
Isobutane
and Nitrogen
Recovery Unit
Purge
Column
Settling Legs
and Product
Take off Valves
Loop Reactor
Powder silo
17 17
Phillips
Phillips
Process
Process
at
at
TVK
TVK
Additivation
Additivation

and
and
Pelletizing
Pelletizing
Extruder hopper
Additive
blender
Premix feeder
Main feeder
CIM
Extruder
Dewatering
screen
Spin dryer
Classifier
Pellet water
tank
Rotary
feeder
Air blower
Pellet water
pump
18 18
Slurry Process
Slurry Process
CSTR
CSTR
-
-

Cascade Stirred Reactor
Cascade Stirred Reactor
19 19
Slurry Process
Slurry Process

CSRT
CSRT
Reactor and Surrounding
Reactor and Surrounding
s
s
20 20
Slurry Process
Slurry Process
-
-
CSTR
CSTR
Process Characteristics
Process Characteristics

Catalyst
Catalyst
:
:
Ziegler
Ziegler
, (
, (
metallocene
metallocene
)
)

Low reaction pressure and temperature
Low reaction pressure and temperature
6 6- -8 8 bar, 70 bar, 70- -90 C 90 C

Reaction heat removed by
Reaction heat removed by
Overhead condensators Overhead condensators
Slurry coolers Slurry coolers
Reactor jacket Reactor jacket

Bimodal product capability
Bimodal product capability
Different molecular weight polymer in 1st and 2nd reactor Different molecular weight polymer in 1st and 2nd reactor
Comonomer built into high molecular weight polymer Comonomer built into high molecular weight polymer

Diluent and polymer separation by centrifuge
Diluent and polymer separation by centrifuge

Diluent cleaning for low polymer removal
Diluent cleaning for low polymer removal
21 21
Process Control
Process Control

Melt index
Melt index

Ziegler catalyst
Ziegler catalyst
[H
[H

2 2

]/[Et]
]/[Et]

MI
MI

Chromium catalyst: T,
Chromium catalyst: T,
[Et], [H
[Et], [H
2 2
]
]
T
T

MI
MI

[Et]
[Et]

MI
MI

[H
[H

2 2

]
]

MI
MI

Density
Density
[comonomer]
[comonomer]

D
D

Molecular weight distribution
Molecular weight distribution

Catalyst type
Catalyst type

Reactors operated at different parameters
Reactors operated at different parameters
22 22
Process Safety
Process Safety

Risk of high volume liquid hydrocarbon
Risk of high volume liquid hydrocarbon

Interlock system
Interlock system
Emergency kill to prevent reaction runaway Emergency kill to prevent reaction runaway except for CSRT except for CSRT
Action valves automatically operated by predefined process Action valves automatically operated by predefined process
parameters to separate/blow parameters to separate/blow- -down equipment down equipment

Closed blow
Closed blow
-
-
down system
down system
Pressure safety valves, blow Pressure safety valves, blow- -down valves release to closed down valves release to closed
system, connected to system, connected to
Flare to burn blown hydrocarbon Flare to burn blown hydrocarbon

Double mechanical seal on pumps in liquefied gas
Double mechanical seal on pumps in liquefied gas
service
service

Gas detectors
Gas detectors

Fire fighting system
Fire fighting system
23 23
Key Equipment
Key Equipment

Reactors
Reactors

Loop
Loop
with axial circulating pump
with axial circulating pump

Gas phase
Gas phase

Decanter centrifuge
Decanter centrifuge

in CS
in CS
TR
TR
only
only

Extrusion line
Extrusion line
24 24
Reactors
Reactors

Loop reactors
Loop reactors

Long jacketed pipe
Long jacketed pipe

straight vertical sections

straight vertical sections
interconnected by elbows at top and bottom
interconnected by elbows at top and bottom

Built in axial pump to circulate slurry
Built in axial pump to circulate slurry

Good surface to volume ratio
Good surface to volume ratio

easy reaction heat

easy reaction heat
removal
removal

Gas phase reactors
Gas phase reactors

Vertical pressure vessel with increased top section to
Vertical pressure vessel with increased top section to
reduce polymer carry over
reduce polymer carry over

Long residence time
Long residence time

Reaction heat removed by external heat exchanger in
Reaction heat removed by external heat exchanger in
recycle gas stream
recycle gas stream

Difficult reaction control
Difficult reaction control
25 25
Loop Reactor Circulating
Loop Reactor Circulating
P
P
ump
ump
26 26
Decanter Centrifuge
Decanter Centrifuge
27 27
CMP Extrusion Line Arrangement
CMP Extrusion Line Arrangement
28 28
CMP Elements
CMP Elements
29 29
Mixing in CMP
Mixing in CMP
30 30
Investment
Investment
Cost
Cost
Basis
Basis
: USGC 2008Q1; 400
: USGC 2008Q1; 400
kt
kt
Technology Solution Gas phase Gas phase Slurry loop Slurry CSTR
Product LLDPE LLDPE HDPE HDPE HDPE
ISBL 126,4 93,8 94,7 114,1 126,8
OSBL 115,3 102,6 102,7 113,7 116,4
Other project cost 131,3 116,5 114,2 123,9 127,3
Total investment 373 312,9 311,6 351,7 370,5
Specific investment,
USD/t
933 782 779 879 926
million USD
31 31
Cost
Cost
of
of
Production
Production
Basis
Basis
: USGC 2008Q1; 400
: USGC 2008Q1; 400
kt
kt
Technology Solution Gas phase Gas phase Slurry loop Slurry CSTR
Product LLDPE LLDPE HDPE HDPE HDPE
Ethylene 1223 1222 1326 1324 1334
Comonomer 176 159 25 24 25
Catalysts&Chemicals 47 14 27 42 22
Additives 13 15 18 18 18
Total raw materials 1459 1410 1396 1408 1399
Power 15 22 25 30 26
Steam 16 2 2 6 13
Other utilities 8 10 6 11 8
Total utilities 39 34 33 47 47
Variable cost 1498 1444 1429 1455 1446
Direct cash cost 14 12 12 14 14
Allocated cash cost 17 15 15 16 17
Total fixed cost 31 27 27 30 31
Total cash cost 1529 1471 1456 1485 1477
USD/t
80%
85%
90%
95%
100%
LLDPE LLDPE HDPE HDPE HDPE
Solution Gas phase Gas phase Slurry loop Slurry CSTR
Total fixed cost
Total utilities
Total raw materials
32 32
Spring Rotary Seal
Ring
Stationary Seal
Ring
Rotary Seal
Packing
Stationary Seal
Packing
Appendix: Typical Mechanical Seal
Product
33 33
Appendix:
Appendix:
Blow Moulding
Blow Moulding
34 34
Appendix: Pipe
Appendix: Pipe
Extrusion
Extrusion