HDPE Slurry Loop Process Technology

HDPE slurry loop process 1

PE History
1933: Explosion of the reactor in the laboratory of MM Fawcett and
Gibson with ethylene at 1400 bars and 170 °C :

This accident generated a white powder : birth of the high-pressure LDPE

1935: In the same conditions , but under control this time, production of 8
grams of LDPE,

1938: Production of the

first industrial ton of
LDPE

1954: Karl Ziegler's

discovery of the
polymerization under low
pressure of monomer by
using organo-metallic
catalysts, giving birth to
HDPE

HDPE slurry loop process 2

PE : Processes to Applications in WE

Processes -----------------------Low pressure------------------------------------------------------- ----High pressure----

5 to 100 barg 1000 to 3000 barg

▪ Slurry (CSTR) Slurry (Loop) Gas Phase Solution Tubular Autoclave

PE Types

HDPE Difference? LLDPE LDPE

In WE 41% 22% 37%

Markets

Pipe Roto-molding Blow molding Other Extrusion Injection Film Coating Other
In WE 7% 1% 16% 6% 12% 52% 4% 2%

HDPE slurry loop process 3

Slurry process overview
Isobutane
make-up

Recycle gas
comonomer Flash
Vent

Flash Lines Isobutane recovery

Purification and recycling

Reactor
Degas
Section
-sing

Nitrogen
Catalyst
cocatalyst
Additives

Purification

Extrusion / Pelletizing

Ethylene Hydrogen Blending/bagging

HDPE slurry loop process 4

Feed preparation: ethylene hydrogenation
Steam
TCV
PCV

C
2
Hydrogenation-
reactor
H
2

To ethylene dryers

Ethylene hydrogenation (acetylene = poison for the polymerization catalyst)

Pd bed , 35 °C, 50 barg

catalyst

C2H2 + H2 → C2H4 (+ H2 → C2H6 )

Safety aspects: Auto decomposition of ethylene, can be initiated by
exothermic heat of reaction
Potential overheating by excess hydrogen
HDPE slurry loop process 5
Feed preparation: ethylene drying

Dryer bed Ethylene

Adsorption on activated alumina

Polar components (H2O, CO, CO2) To flare To flare

Hot nitrogen regeneration >200°C

Flow: top down

Safety aspects:
Heat released at initial saturation with
hydrocarbons Ethylene dryer Ethylene dryer

Link between electrical heater and

Nitrogen
potential source of hydrocarbons Dried ethylene

HDPE slurry loop process 6

Feed preparation: hexene degassing
Cooling water
To flare

Hexene

Distillation
Column

Steam
Kettle-accumulator

Degassed hexene
Hexene degassing
Accumulated moisture due to unloading procedures or light
hydrocarbons
Safety aspects : Unloading procedure of utmost importance

HDPE slurry loop process 7

Feed preparation: IC4 hydrogenation & stabilization
Hydrogenation Stabilisation

Cooling water
To flare
TCV
Hydrogenation reactor

Steam

Storage sphere
1
1
1 Distillation column
1
iC4
1
Fresh hydrogen Cooling water
Steam Reboiler

Cooling water
Degassed isobutane
C4 storage

Hydrogenation and stabilization

Hydrogenation of unsaturated hydrocarbons (120°C adiabatic over Pd
catalyst; iC4 gas; 15 barg (formation of coke to be prevented (short
residence time); iC4 condensed and H2 recovered)
& Stabilization of the iC4 (light hydrocarbons vented at 80°C;
14 barg) => fresh isobutane
HDPE slurry loop process 8
Feed preparation: IC4 hydrogenation & stabilization

Safety aspects:

Hydrogen: invisible and auto-ignition when leaking

(H2 expansion heats up the gas)

Potentially dangerous exothermic reaction

(note: not core reaction so process running in background!!!)

MOC :

small changes can have huge consequences

(composition, accumulation,…)

HDPE slurry loop process 9

Feed preparation: Isobutane drying
Isobutane

Dryer bed
Adsorption on 13X (molecular sieve – To flare To flare
zeolite)
Polar components (H2O, CO, CO2)

Hot nitrogen regeneration >200°C

Flow: bottom up

Safety aspects:
Isobutane dryer Isobutane dryer
Heat released at initial saturation with
hydrocarbons Nitrogen Dried isobutane
Link between electrical heater and
potential source of hydrocarbons

HDPE slurry loop process 10

Feed preparation: Chromium catalyst activator
Catalyst activator
▪Gas-fired or electrically
heated
▪Fluidized bed
▪Activation by air

Safety aspect:
▪Chromium catalyst is
carcinogenic
▪External spills to be
prevented (special
sintered filtering devices)
Risk perception as a function of habit :
“complacency”

HDPE slurry loop process 11

Feed preparation: Chromium catalyst activator
Catalyst activation temperature profile : very important for MFI control
ATOFINA FELUY SA
Dépt Production PE
JMD/fl - Log 193.92

CONSIGNES D'ACTIVATION TYPE : TEQ pour grades 38140 - 34150 - Date : 03.03.2005 - REV. 0

Température Débit
CHARGE ( ° C) (Nm³/h)

C25305 1 fût = 50 kg
Terhel 963 175 kg
635 °C [1]
610°C

TOTAL : 225 kg 560°C

[2] = [1] - 50°C
C25305 1 fut = 50 kg
Tergel 963 IBC / fut = 45 kg

PROGRAMME
360°C
1. Type 2
300°C
270°C
2. T° palier (°C) 635
47.5
3. Durée palier (h) 6
[3] 41
4. Pente montée 1
(°C/min) 120°C
5. Débit 1 (Nm³/h) 47.5
Temps (h)
6. Débit 2 (Nm³/h) 41
3 7.3 8.3 9.3 15.3 18.5 19.5
7. T° chang. Débit 300
Azote Air Azote

Chargement Déchargement

[1] TIC 2153 Température activateur (°C)

[2] TIC 2157 Température préchauffeur (°C)
[3] FIC 2152 Débit d'air ou d'azote de fluidisation (Nm³/h)

HDPE slurry loop process 12

Catalyst and cocatalyst

Catalyst :
▪ Three types of catalysts
▪ Three types of catalyst dosing systems

Basis for different design types

▪ Catalyst has an induction period or not

▪ Catalyst granulometry prevents transport under “mud” form

▪ Original design is the chromium mudpot

▪ New design of ZN catalyst due to absence of induction period and poor
flow-ability of catalyst
▪ Metallocene design based on chromium mudpot but low pressure

HDPE slurry loop process 13

Catalyst induction period

Activity

Ziegler-Natta
or metallocene
catalyst
Chromium
catalyst

Industrial
Residence
time

Induction time
period

HDPE slurry loop process 14

Catalyst and cocatalyst
BAGFILTER

Chromium catalyst
HP FRESH
system:
▪ Good flow-ability
▪ Induction time MS4002
▪ High pressure iC4
▪ Catfeeders 1D 2D 3D

Safety aspects
D1 D2 D3 D4 D5 D6
▪ Chromium carcinogenic
▪ Only 1 manual isolation
valve between atmosphere
and high pressure iC4 of CHROMIUM
mudpot (human error) CATALYST XV4283D XV4285D
▪ Don’t be fooled by induction
TO
time! REACTOR

HDPE slurry loop process 15

Catalyst and cocatalyst
ZIEGLER-NATTA
CATALYST

Ziegler Natta catalyst:

XV4111B
▪ Poor flow-ability so dilute system
▪ Make up tank and feed tank
XV4113B

XV4114B XV4109B

MS441
PICA4118B
FLARE ▪ Nitrogen pressurized
PICB4118B
XV41419B ▪ Catalyst feeding by pumps
N2
XV4123B
M M
FIC4120B
PIC4125B

MS439 MS440A
XV4121B

M PD414I
Safety Aspects
PC405A/B/C/D

FRESH C4
FIC4178B FIC4168B
▪ Catalyst has no induction period
So must prevent too much
PIC4131B

M
catalyst from entering reactor at
PD414J
all times
XV4289E
XV4288E

GF432A/B PD414C/D

NAAR RxA
NAAR REACTOR ▪ So feed tank is at lower
MS442
pressure than reactor, pumps
have limited capacity

HDPE slurry loop process 16

 Catalyst and cocatalyst Metallocene catalyst:
▪ Good flow-ability so storage under mud
METALLOCEEN form
CATALYST
▪ Nitrogen pressurized
CONTAINER

▪ Mixing vessel for guaranteeing

MS402N

MS402O
constant concentration
▪ Catalyst feeding by pumps
GY402B3
▪ Solvent is Olefin free or fresh IC4
GY402B4

M PD414I
M

FIC4178B FIC4168B
FRESH C4

MS439B TIBAL
Safety Aspects
M
▪ Catalyst has no induction period
MS437B

PD414J

XV4281B
XV4282B
MS437
So must prevent too much catalyst
BRANDKAMER
RxB CAT.

PD414C/D
NAAR REACTOR B
from entering reactor at all times
FLARE
NAAR REACTOR A
So mixing vessel is at lower pressure
MS437B
STOOM
than reactor, pumps have limited
N2
COND
capacity
▪ Prevent reaction by residual ethylene
or hexene
▪ Catalyst is pyrophoric and water
reactive
HDPE slurry loop process 17
Catalyst and cocatalyst
N2 TIBAL 60%

PIC4037E
Co-catalyst:

MIN. OIL
▪ TIBAL & DEZ (organometallic compounds)

XV4000E

XV4077E

XV4004E

XV4005E
▪ Different concentrations 10,20,60% MS428E

XV4068E

HV4070E
▪ +/-25% pyrophoric limit
XV4047E XV4049E

XV4076E

XV4006E
XV4002E

XV4048E
Safety precautions:
GW425A GW425B

▪ Burning pit
XV4091E
▪ Firewalls separating vessels and pumps NAAR
MS428E
▪ Sloped floors
▪ Well ventilated area MS425C

▪ Prevention for accumulation of rain

XV4093E
▪ Welding procedures with fuse tube and M PD425E

automatically closing valves ZN-CATALYST

M PD425D CATFEEDERS

▪ Emergency stop with depressurization of

containers M PD425F ZN-CATALYST
CATFEEDERS

HDPE slurry loop process 18

The reactor section
Main components:

feed line, reactor, circulation pump, jacket and coolant,

settling legs, flash lines, flash tank
Reactor

Cooling Jacket

Steam

Recycle isobutane
Ethylene
Hexene
Hydrogen
Anti-fouling Cooler
Coolant
Drum
Killing gas Gas recovery

Flash
Tank
Settling Legs Flash
Circulation pump
Fresh isobutane PTO valves Line(s)
Catalyst
Finishing

HDPE slurry loop process 19

Polymerization reactor

HDPE slurry loop process 20

The reactor section: cooling
The reaction is exothermic:

n (CH2 = CH2)  - (CH2 - CH2)n - + 3344 kJ/kg (1 MW per t/hr)

U-rate heat transfer rate over jacket wall

Re = r u d
m hw Wall transfer coefficient = kw
e

Pr = m Cp hwf fouling transfer coefficient = kwf

k ef

kw = k for carbon steel = 35 W / m.K

Nu = (0.023)(correction factor) Re0.8 Pr 0.33
e = wall thickness = 20 mm
kwf = k mean of H&LDPE = 0.418 W / m.K
ef =fouling thickness = 0.015 mm
h= Nu . k
d
The jacket wall is the largest contributor
to the heat transfer resistance !

HDPE slurry loop process 21

The reactor section: cooling
Coolant loop
▪ Control of temperature with a precision of 0.1 - 0.2 °C
▪ Constant coolant flow
▪ Control delta T (Reactor-Coolant) (Q = U*A*deltaTln)

▪ Closed loop
▪ Surge vessel Pressurized by nitrogen (only DP by pump)

HDPE slurry loop process 22

The reactor section: cooling
feeds cata

feeds cata

cata
feeds

feeds cata

HDPE slurry loop process 23

The reactor section: Cooling/Fouling
Deposition of low MW material if walls are
too cold

Melting of polymer and deposition on the

walls if reactor temperature is too high

For an industrial size reactor, cleaning takes

3 weeks and the financial loss due to non-
productions can reach 3-4 million EUROS

U-rate reactor A 28 Jun - 2 Oct 03

U-rate reactor A 23 Oct - 3 Dec 03
U-rate rA May-Dec 2005

1400

1200

1000

800

600

400
1
10
19
28
37
46
55
64
73
82
91
100
109
118
127
136
145
154
163
172
181
190
199
208
HDPE slurry loop process 24
The reactor section: Cooling/Fouling
The reactor wall can be prone to fouling

Fouling is a multifactorial phenomenon linked to temperature, solids

concentration, comonomer concentration…

Global Heat Exchange Coefficient

[W/m2.K]

Model

Measured

HDPE slurry loop process 25

The reactor section: Circulation pump

The circulation pump:

▪ Maintain the suspension at all times

▪ Turbulence creates intimate contact between catalyst and monomer
▪ Velocity in reactor ~10 m/s is the basis for good heat exchange on internal
side of reactor

Safety aspects:
▪ Typically, the seal of a centrifugal pump is a weak part and is likely to leak
eventually
▪ Double or triple seal design
▪ Flushing fluids

HDPE slurry loop process 26

The reactor section: Circulation pump

HDPE slurry loop process 27

The reactor section: Circulation pump
Mechanical seal cartridge, either double or triple

HDPE slurry loop process 28

The reactor section: Circulation pump

Reactor homogeneity

Same concentration profile along

reactor

Circulation time is of utmost

importance.

Limited to ~10-12 m/s

Challenge for debottlenecking

No axial mixing in the reactor: Local PFR behaviour

inhomogeneities can stay for a
long time! Overall CSTR behaviour

 Multiple feed lines

HDPE slurry loop process 29

The reactor section: Gas Cap Limitations

Gas cap limits

11

10
34150
9
38140 42170
0% H2
% C2 OG

47100
8 0.15% H2
49090 53080
ER2245 0.3% H2
3802
46110 5203 0.6% H2
7
53140

6
5702
52021
5
85 90 95 100 105 110
RX temperature

HDPE slurry loop process 30

The reactor section: Settling legs

PTO (Product Take-Off) valves

HDPE slurry loop process 31

The reactor section: Settling legs

Big reliability problems of the PTOs have

led to prefer a continuous take-off (CTO)

HDPE slurry loop process 32

The reactor section: Settling legs

HDPE slurry loop process 33

The reactor section: Settling legs

HDPE slurry loop process 34

The reactor section: Flashlines

Flash lines:
▪ Objective to flash all liquid while
maintaining the polymer
temperature at best degassing
temperature
▪ Consist in steam-jacketed pipes
▪ Low pressure steam
▪ Dynamics of the flashing
phenomenon, linked to the settling
legs, makes design difficult with
PTO valves

Safety aspects
▪ Prevent presence of liquid
isobutane after flash
▪ Very dangerous when liquid is
conveyed to extruder

HDPE slurry loop process 35

Degassing: purge column
Monomer, solvent/diluent and co-monomer solubility in PE
Sam = (1/kam).pi

Sam is the solubility in the amorphous fraction of the polymer, (mol/liter PEamorphous)
kam is the Henry’s law constant, (bar / l amorph. polymer / mol)
pi is the partial pressure of the gas around the polymer, (bar )

Arrhenius law
Sam = S0,am exp (-Ea / RT)

Sam is the solubility in the amorphous fraction

of the polymer, (mol/liter PEamorphous)

Ea Activation energy,(J.mol-1)
R Ideal Gas constant: 8.314 (J.mol-1.K-1)
T Temperature, (K)

HDPE slurry loop process 36

Degassing: purge column
Minimum flow of nitrogen
▪ Assumption is that the partial pressure of species to be degassed in the
nitrogen exiting the purge column must be lower or equal to its partial
pressure in the flash tank.
(pi(C6) /(pi(N2)+ pi(C6)+ pi(IC4)+pi(C2))) purge column< (pi(C6) / (pi(C6)+pi(IC4)+pi(C2))) flashtank

▪ Equilibrium conditions assumed

Maximum nitrogen flow
▪ Based on the minimal fluidization velocity
▪ Typical limitations 2-3 cm/s
Nitrogen temperature
▪ Heating the gas helps, but not a lot, since its Cp is low
Fluff temperature
▪ Keeping the fluff as hot as possible helps a lot (flash lines)
Residence time
▪ Only plays a role if the other criteria are satisfied

HDPE slurry loop process 37

Finishing
Additives :
• Antioxidants (thermal stability)
REACTOR • U.V. stabilisers (light stability)
• Antistatic agents (static electricity
dissipation)

Pigments (colour)

POWDER
+ additives
+ additives
(+ pigments)

PELLETS POWDER
(COMMERCIAL FLUFF)

HDPE slurry loop process 38

Finishing section

HDPE slurry loop process 39

Plant layout
Lavéra PP unit

Reaction
30% of plot space
Degassing
Extrusion
Blenders+Silos 70% of plot space
Conditioning
& Pallets storage

HDPE slurry loop process 40

Extrusion building

Extrusions feed silos can be located on top of building

HDPE slurry loop process 41
Extrusion lines : basic scheme

HDPE slurry loop process 42

Extruder / Mixer

Solid material (powder or pellets)

Molten polymer

HDPE slurry loop process 43

Extruder / Mixer

Gate
section

Gear Drive end Feed

reducer section section

Mixing Water end

section Vent section section

Discharge
section

HDPE slurry loop process 44

Screw : Assembly of elements

HDPE slurry loop process 45

Extruder / Mixer

Start-up
diverter Pelletizer
Gear
Pump Motor
(Option)
(KNT)

Diverting
Valve

Mixer Dual-Bar Under water

Screen pelletizer
(LCM) Changer
(UP-N)
(KSD)

HDPE slurry loop process 46

Gear Pump
3D cross section of a Polyrex melt pump (Maag)
Lubrication by the molten polymer

HDPE slurry loop process 47

Dual bar filters

Die Plate

HDPE slurry loop process 48

Pelletizing : Die Plates

Low-Pressure-Design structure
allows both low extrusion
pressure and high throughput.

Internal vacuum insulation structure close to the die face

and superior heat transfer through wide heat channels
running as close as possible to the die nozzles from cooling
down in the circulating pellet cooling water

A typical die plate has 1500 to 10000 holes

HDPE slurry loop process 49
Pelletizing

HDPE slurry loop process 50