PP Technology

Content
 Introducing PP
 Application
 History
 Ziegler-Natta polymerization
 Catalyst development
 PP processes
 Process control
 Process safety
 Key equipment
 Investment cost
 Cost of production
2
 Introducing PP
 PolyPropylene – stereoregular, crystalline polymer
 Homopolymers
 Random copolymers with 0,5-4% ethylene content
 Impact (block, heterophasic) copolymers with 5-20 % ethylene
content
 Terpolymers - with second comonomer
 Characteristics
 Melt index 0,3->100 g/10 min (230 C/2,16 kg)
 Melting point 142 – 165 C
 Polydispersity (TVK grades)
 3,5 – 5 reactor products
 2–3 controlled rheology (CR) products
 Broad range of mechanical properties

3
Application

3,0 PP end-use
7,6
19,4
1,0
film
fibre
blow moulding
injection moulding
extrusion coating
other extrusion

39,6 others
27,8

1,6

4
Application by Properties

HECO
SHEET
INJECTION
MOULDING
RANDOM

FILM
FIBER
HOMO FIBER melt blown
PIPE

0,1 1 10 100 1000 10000

MI, g/10 min/230 C

5
History
 Discovered by Giulio Natta and Karl Rehn in 1954
 First industrial process developed by Montecatini in 1957
 Catalyst is the driver for process and product
development
 Licences available for 400 kt/y capacity single lines
 Consumption in 2012
 Global: 52 million t
 Domestic: 157 thousand t
 TVK PP plants
 1978 60 kt/y Hercules slurry process, shut down in 1993
 1982 50 kt/y Sumitomo bulk process, shut down in 2002
 1989 60 kt/y Spheripol process, debottlenecked to 100 kt/y
 1999 140 kt/y Spheripol process, debottlenecked to 182 kt/y
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Ziegler-Natta Polymerization 1

Propylene polymerization
Ziegler - Natta catalyst preparation

1. Base support MgCl2 1. ZN catalyst

Al-alkyl External donor

2. Activation
(e.g. silane)
TiCl4 Internal donor
2. Titanation
(e.g. phtalate)

Propylene
3. Polymerization

3. ZN catalyst
4. PP product

7
Ziegler-Natta Polymerization 2

8
 Catalyst Development
Generation Catalyst Productivity X.I. Remarks
(year) composition (kg PP/g cat) (%)
1st δ-TiCl3*0,33AlCl3 2-4 90-94 No morphological control,
(1954) + AlEt2Cl deashing and atactic removal
necessary
2nd δ-TiCl3 + AlEt2Cl 10-15 94-97 Granular catalyst, deashing
(1970) necessary
(1968) MgCl2/TiCl4 + AlR3 40 First MgCl2 based catalyst for PE,
very low stereocontrol
3rd MgCl2/TiCl4/Benzoate 15-30 95-97 First MgCl2 based catalyst for PP,
(1971) + AlR3/Benzoate low stereocontrol, low H2
response, broad MWD
4th MgCl2/TiCl4/Phtalate 40-70 95-99 Spherical catalyst with controlled
(1980) + AlR3/Silane porosity, medium-high
stereocontrol, medium H2
response, medium MWD
5th MgCl2/TiCl4/Diether 70-130 95-99 Same as 4th generation but very
(1988) + AlR3/Silane (opt.) high activity, narrow MWD,
excellent H2 response
6th MgCl2/TiCl4/Succinate 40-70 95-99 Same as 4th generation but
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(1999) + AlR3/Silane broad MWD
PP Processes
 First PP process: slurry phase technology
in stirred tank reactors; numerous process
steps necessary
 Deashing to remove catalyst residues
 Atactic PP removal
 Up-to-date processes: few process steps
only
 Bulk or gas phase polymerization
 Catalyst residues and atactic PP removal not
necessary

10
PP production
simplified block diagram

Polymerization of Polymer and Polymer Additivation and

homopolymer/random monomer separation and pelletizing
copolymer separation cleaning

Raw material
preparation and
treating Polymerization of block
copolymer

11
Slurry Technology
Early PP Process – Not used today

12
Spheripol Process
Typical process parameters
Process step Temperature, C Pressure, bar

Catalyst activation 10 40

Prepolymerization 20 35

Polymerization - loop reactor 70 34

High pressure separation 90 18

Polymerization - gas phase 75-80 10-14

reactor
Steaming 105 0,2

Drying 90 0,1
13
Spheripol Process
Polymerization
Catalyst Precontacting
HP Flash Separator
Donor Copoly Reactor

TEAL Loop Reactor

Prepoly Reactor
S

Flash Line

Slurry Pump SC

Gas blower

Propylene Recovery Ethylene

Hydrogen and Purification

Hydrogen

Propylene LP Separator

S
Steamer

Nitrogen
Dryer

PP Powder
to Extrusion

14
Spheripol Process
Additivation and Pelletizing

15
Unipol Process
Polymerization

65-70 C
25 bar

16
Unipol Process
Degassing and Recovery

17
Chisso Process
Packed Gas Phase Reactors

18
Spherizone Process

19
Spherizone Process
Multizone Reactor Principle

20
Spherizone Process
Extended Product Properties
Broad MWD
35

Pressure pipe Maximum stiffness

classification Homopolymer
PP-R 125 2550 MPa flexural modulus

Impact-Stiffness balance
HECO: 5 KJ/m2 Izod
Random
1650 MPa flexural modulus
Minimum brittle
-3 C transition
temperature Spherizone
2,3 Spheripol
Narrow MWD
Gas phase

21
Process control

Melt index H2 concentration in reactors

Isotactic index external donor (alkyl/donor
(stereoregularity) ratio)

MWD different H2 concentration in

reactors, catalyst
Raco ethylene content ethylene feed

Heco ethylene content residence time, C2/C3 ratio in

GP reactor

22
Block copolymer
C2 content vs gas composition
75 68
73 CXS(BIP)
66
71 C2(BIP)
Bipolymer C2 content, %

Bipolymer CXS, %
69
64
67
65 62
63
60
61
59
58
57
55 56
0,35 0,37 0,39 0,41 0,43 0,45 0,47 0,49
C2/(C2+C3) m ol ratio

23
Process Safety
 Risk of high volume liquid hydrocarbon
 Interlock system
 Emergency kill to prevent reaction runaway
 Action valves automatically operated by predefined process
parameters to separate/blow-down equipment
 Closed blow-down system
 Pressure safety valves, blow-down valves release to closed
system, connected to
 Flare to burn blown hydrocarbon
 Double mechanical seal on pumps in liquid propylene
service
 Gas detectors
 Fire fighting system

24
Key Equipment

 Reactors
 Loop with axial circulating pump
 Gas phase
 Gas circulating blower/compressor
 Extrusion line

25
Gas Circulating Blower

26
Investment cost
Basis: WE 2010 Q1

PP HOMO PP HECO
Process Bulk Bulk+gas phase
Capacity 325 kt 325 kt
Investment, million EUR
ISBL 93 102
OSBL 47 51
Total investment 140 153

Specific investment cost, EUR/t 431 471

27
 Cost of Production
Basis: WE 2010 Q1; 325 kt

PP HOMO PP HECO
Process Bulk Bulk+gas phase 100%
Capacity 325 kt 325 kt
90%
Propylene 865,8 796
Comonomer 80 80%
Catalysts&chemicals 24,9 24,9
Total raw materials 890,7 900,9 70%

60% Total fixed costs

Power 24,1 26,3
Other utilities 15,9 15,9 Total utilities
Total utilities 40 42,2 50% Total raw materials

Direct fix costs 17,1 17,1 40%

Allocated fix costs 13,6 13,6
Total fixed costs 30,7 30,7 30%
Bulk Bulk+gas phase
Total cash costs 961,4 973,8

28
Appendix: BOPP Film Production
Stenter Process

29
Appendix: Injection Moulding

30