EFFECT OF IMPURITIES ON POLYMERISATION REACTION OF ETHYLENE BY

ZIEGLER NATTA CATALYST IN HDPE PLANT and MITIGATION - A CASE STUDY

[Krishna Kumar, Manager, CPF 15866, HDPE 2]

[Contact: 34228/30309]

Abstracts

HDPE II, a Low Pressure Slurry Process technology (provided by Mitsui, Japan) based plant
with 1 Lakh ton per annum installed capacity produces HDPE polymer. At some point of time
during prolonged running of F55HM0003N (Film grade) abnormal reaction conditions have
appeared and necessitated reaction shut down for taking fresh start up. F55HM0003N falls
in category of series grade where 2 CSTR reactors remain associated in series in which
slurry from first reactor goes to 2nd reactor. Catalyst is fed only to 1st reactor. Their effect on
reaction is characterised by increase in Ethylene (C2) % in PGC data and reactor pressure.

Detailed analysis suggested that some foreign materials must be interfering with catalyst and
co-catalyst (Ziegler-Natta catalyst) and deactivating them, thereby causing insufficient
reaction of ethylene inside reactors. Therefore, a detailed study performed, to analyse the
undesired materials that may slip in within reactors with raw materials or through any other
possible route and their effects on this reaction system. These undesired materials could be
CO, CO2, H2O, Acetylene, Br-, S etc.

Detailed study revealed that undesired materials must be causing deactivation of catalysts,
largely the co-catalyst, thereby causing decrease in TEAL/PZ ratio in reactor, which must be
further causing insufficient reaction of ethylene. Increasing TEAL feeding to 1st reactor by
certain calculated amount to improve AT/PZ ratio has been highly helpful in containing such
reaction conditions and in some cases it has prevented unnecessary plant S/D. However, it’s
always better to keep those undesired materials within permissible limit in the first place than
using mitigation steps for containing such reaction abnormalities.

1. Introduction:

HDPE II, a low pressure slurry process technology ( technology provider- Mitsui, Japan)
based plant with installed capacity 13.3 TPH produces HIGH DENSITY POLY
ETHYLENE POLYMER (HDPE) .Here, frequently produced grades are F55HM0003N
(Film), E52A003N & E52U003N (Extrusion grade), P54A001N(Pipe) and W55A004N
(Rafia). During production of F55H0003N grade at some point of time it has been observed
that MFR of Reactor 1 and pellets starts to decrease.

Before delving into details of this problem it is necessary to understand some important
points related to this grade in following table:

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 GRADE: F55HM0003N
FEED: C2H4, H2, Butene-1
Catalyst: PZ- TiCl4 Co-Catalyst: AT (TEAL) – Et3 Al
Pellet MFR: 0.07-0.09 Reaction medium: Hexane
Density: 0.952-0.955 R 1 (RB 201) R 2 (RB 221)
MFR: 800-900 ( 0.14- 0.19)
PZ Concentration (mmol/lit hexane): 0.085 -
AT Concentration (mmol/lit hexane): 0.5 -

Objective of this paper is to investigate the reasons behind this kind of problems and suggest
mitigation steps to control this kind of problems. Therefore, chemical compounds that may
enter into reaction in any possible way have been first identified and their effects on reaction
system have been studied. Further, based on theoretical studies, mathematical calculations
have been performed and mitigation steps have been suggested for controlling such abnormal
reaction condition.

This study supported by a case study for kind of problem has been included where reaction
abnormality has been arrested using suggestions made through this study. However, there are
many instances of such improvement in abnormal reaction conditions based on suggestions
made. In the end results, suggestion and scope for further study on this issue has been
presented.

2. Main Content

2.1 Effect of Impurities/ Undesired material – through reaction mechanism

As it is known that while polymerisation reaction of Ethylene using Zeigler Natta catalyst
first of all COMPLEX 1 forms and then ethylene addition starts on this intermediate complex
which leads to formation of COMPLEX 2 at any point of time and this complex keeps on
propagating before termination of this polymer chain that is being propagated. Therefore, any
of the impurities reacts selectively with one of the intermediate complexes 1, complex 2,
TEAL or PZ will inhibit this polymerisation reaction. AT reacts violently with water,
alcohols, phenols, amines, carbon dioxide, sulfur oxides, nitrogen oxides, halogens, and
halogenated hydrocarbons, causing fire and explosion hazards (Handling Chemicals Safely,
Vereniging 1980 p. 929). Two blank boxes on TiCl4 structure representing 2 empty 3d
orbitals of Ti.

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i) Effect of Acetylene

Acetylene being a highly reactive hydrocarbon may act as a inhibitor by interacting with
TEAL as well as complexes 1 and 2 that are formed during polymerisation. While the first
insertion of acetylene to yield Et2Al-CH=CHCH2CH3 is reasonably facile, subsequent
insertions into the Al-alkenyl bond occur only under more forcing conditions (Samuel Stefan
Karpiniec, 2010).

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 ii) Effect of Sulphur

Sulphur mainly acts as an inhibitor by reacting with complex 2 as well as with TEAL in this
ethylene polymerisation reaction (Nederlandse Vereniging, 1980). Same type of inhibition
is also shown by Phosphorous.

iii) Effect of CO

Carbon mono oxide acts as an inhibitor by reacting with complex 2 as well as with TEAL in
this ethylene polymerisation reaction (Nederlandse Vereniging, 1980).

iv) Effect of CO2

Carbon di oxide acts as an inhibitor by reacting with complex 2 in this ethylene

polymerisation reaction. It also reacts with co- catalyst TEAL present Zeigler Natta catalyst
system shown in 2nd reaction (Nederlandse Vereniging, 1980).

v) Effect of Bromide

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vi) Effect of water molecule (moisture)

Water molecule is having very high affinity with Tri-ethyl –aluminium present in Ziegler
Natta catalyst system. It may also react with complex 1 and 2 but not as violently as with
TEAL.

The overall reaction mechanisms for the interaction between tri-ethyl-aluminum with H2O
can be written as follows:

In these reactions, pair of reactions in step 1 are exothermic and can readily occur, whereas in
the step 2 processes are endothermic and thus more difficult to achieve. The barrier to
formation of CH3-CH2AlO is not easily overcome at the ambient temperature.

2.2) Insight of this problem

Impurities for this polymerisation reaction can be classified into inert impurities and reactive
impurities. Inert impurities do not participate in reaction but they pose difficulties by
increasing reactor pressures (both reactors). Examples are Methane, Ethane etc.

Whereas reactive impurities participate in reaction and consume catalysts or the intermediate
complexes formed during reaction. Their effect on reaction is characterised by increase in C2
% in PGC data and reactor pressure. In series grade, their impacts are larger on 2nd reactor as
compared to 1st reactor because as catalyst is directly being fed to 1st reactor, so most of the
catalyst molecules are consumed in 1st reactor. This leads to highly insufficient supply of
catalyst to 2nd reactor and that too is consumed by these impurities. Examples are CO, CO2,
Suplur, Moisture etc.

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Slipping in of impurities (undesired materials) that used to deactivate catalyst causes decrease
in [AT/PZ] ratio in Reactor. Thereby, causing insufficient amount of remaining [PZ-AT]
intermediate complex required for polymerisation reaction.

Insufficient intermediate [PZ-AT] complex could polymerise only small part of ethylene and
remaining ethylene was just increasing ethylene concentration in reaction.

That's why C2% trend shown by PGC keeps on increasing during this reaction disturbance.
Co-catalyst (TEAL) has double effect- first, it eliminates impurities from different reaction
components and second, it activates the main catalyst as it reduces Ti4+ to the active Ti3+ form
(Suba, Arva and Nemeth, 2007). Therefore, for improving such conditions TEAL flow
should be increased and some amount of PZ is also being neutralised as shown in reactions
above. Hence, PZ flow should be increased to some extent.

It can be understood from above fact that AT/PZ ratio is highly important for tackling
undesired materials causing deactivation of co-catalyst & PZ (to some extent). Basically,
large AT/PZ ratio means large amount of TEAL i.e TEAL Conc -m mol/ lit of HX for every
PZ molecule to form complex. With increasing amount of TEAL more impurities can be
eliminated and more active sites can be formed, productivity of catalyst increases (Suba,
Arva and Nemeth, 2007).

Large amount of TEAL will ensure that even after de-activation by undesired materials
sufficient TEAL is present to form intermediate complex with PZ. Therefore, for same
amount of such undesired impurities F55HM0003N grade will be highly vulnerable to
disturbances as compared to B52A003N and lastly B63A003N (follow table ).

GRADE R1 R2
PZ AT AT/PZ PZ AT AT/PZ
F55HM0003N 0.085 0.5 5.9 - - -
B52A003N 0.039 0.5 12.8 - - -
B63A003N 0.022 0.5 22.7 0.011 0.5 45.5
W55A004N 0.011 0.5 45.5 0.011 0.5 45.5
E52U003N 0.039 0.5 12.8 - - -
Table: AT/PZ ratio based comparative analysis for vulnerability to disturbances for different
grades

Appropriate amount of Catalyst and Co-catalyst feeding for such conditions can be calculated
using various available parameters.

2.3) Calculations:

To calculate extra TEAL feeding required in such case to improve [AT/PZ] ratio should be
discussed in 3 parts:

a) TEAL flow that is needed to improve already exhausted co-catalyst into reactors
because of these undesired materials. This problem will start to occur when
TEAL/PZ ratio goes below 1 because in such cases co-catalyst will be less in

6
 proportion by mole to main catalyst to form sufficient amount of intermediate
complex. Here, theoretically prescribed TEAL/PZ ratio 5.9 for F55HM0003N garde.
So, extra TEAL flow need to bring back TEAL concentration to 0.5 in reactor 1 (RB
201) to normalize reaction condition.
Calculation of hexane in reactor at any point of time during reaction

Reactor volume = 90 m3

Till overflow volume = 58 m3 (solid+ liquid+ gas)

Total volume available for liquid and solid till overflow line excluding void space due to
gas (15%) in it = 49.3 m3

Since, 1st reactor has slurry concentration 400 gm PE/lit of Hexane.

Hexane = (34.725 m3) * (0.6 MT/m3) = 20.835 MT

P.E. = (14.575 m3)*(0.953 MT/m3) = 13.89MT

TEAL solution concentration: 200 mmol/lit hexane

Hexane density under prevailing condition: 0.65 𝑔𝑚/𝑐𝑚3

(34.725 𝑚3 ) × (0.5 − 0.085) × 0.65 𝑔𝑚/𝑐𝑚3

Extra TEAL solution, 𝑓𝑀𝑂 (𝑘𝑔) =
200 𝑚𝑚𝑜𝑙 ⁄𝑙𝑖𝑡 𝐻𝑥

𝑓𝑀𝑂 , is the minimum amount, in kg, of TEAL solution feeding needed to bring back
TEAL concentration in R1 to normal concentration 0.5 mmol/lit hx.

b) Extra TEAL feed needed on account of moisture in fresh Hexane if its greater than 5
ppm (as per design specification)
If x be the actual moisture content in Hexane from hexane dryer outlet (VV703) then

Extra moisture = (X-5)/18 mole per ton Hexane feed

Slurry concentration: 400 gm P.E. /lit. Hexane in 1st reactor and 350 gm P.E. /lit. Hexane
in 2nd reactor

Hexane density under prevailing condition: 0.65 𝑔𝑚/𝑐𝑚3

Total fresh Hexane feed to 1st reactor (RB 201)

𝑝𝑙𝑎𝑛𝑡 𝑙𝑜𝑎𝑑(𝑡𝑝ℎ) × (𝐵𝑙𝑒𝑛𝑑 𝑟𝑎𝑡𝑖𝑜 𝑖𝑛 𝑅𝐵 201) × 0.65 100 − 𝐷𝐶1%

𝐹𝑅1 = [ 𝑔𝑚 ]×( )
400 100
𝑙𝑖𝑡. ℎ𝑒𝑥𝑎𝑛𝑒

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 Total fresh Hexane feed to 2nd reactor (RB 221)

(𝑝𝑙𝑎𝑛𝑡 𝑙𝑜𝑎𝑑) × 0.65 𝑝𝑙𝑎𝑛𝑡 𝑙𝑜𝑎𝑑 × (𝐵𝑙𝑒𝑛𝑑 𝑟𝑎𝑡𝑖𝑜 𝑜𝑓 𝑅1) × 0.65

𝐹𝑅2 = [ − 𝑔𝑚 ]
350 × 10−3 400
𝑙𝑖𝑡. ℎ𝑒𝑥𝑎𝑛𝑒
100 − 𝐷𝐶2%
×( )
100

(𝑥 − 5) × (𝐹𝑅1 + 𝐹𝑅2 ) × 0.65

Total moisture entering into reactor system =
18
(𝑥 − 5) × (𝐹𝑅1 + 𝐹𝑅2) × 0.65
Extra TEAL feed, 𝑓𝑀 =
(𝑀𝑜𝑙. 𝑤𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟) × (200 × 10−3 𝑚𝑜𝑙 ⁄𝑙𝑖𝑡 𝐻𝑥)

c) Extra feeding of TEAL needed on account of such impurities like acetylene, CO, CO2
etc.
If Y ppm be the amount of such impurity and as one mole of these impurities react with
one mole of co-catalyst or intermediate complex then

𝑔𝑚
𝑥(𝑝𝑝𝑚) × 𝑝𝑙𝑎𝑛𝑡 𝑙𝑜𝑎𝑑(𝑡𝑝ℎ) × 0.65( )
𝑓𝐼 = 𝑚3
(𝑀𝑜𝑙. 𝑤𝑡 𝑜𝑓 𝑢𝑛𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙) × 200 × 10−3 𝑚𝑜𝑙 ⁄𝑙𝑖𝑡 𝐻𝑥

Total TEAL feed, F = 𝒇𝑰 + 𝒇𝑵 + 𝒇𝑴 + 𝒇𝑴𝑶

𝑓𝐼 : TEAL flow on account of impurities excluding water (kg/hr)

𝑓𝑁 : Teal flow in normal condition (kg/hr)

𝑓𝑀 : TEAL flow on account of moisture (kg/hr)

𝑓𝑀𝑂 : Minimum amount of TEAL solution (AT+ Hexane) required on account of already
deactivated co-catalyst (kg)

2.4) Mitigation Steps

a) Controlling abnormal reaction

First aim should be to make –up already exhausted catalyst and co-catalyst that have been
consumed by impurities. Total make up amount of catalyst and co-catalyst can be disturbed
over period of 2 hrs or more. Signs of improvement in reaction should start to appear after
this make-up. Improvement in reaction will be indicated by (C2% in PGC reading, it should

8
become steady or start to decrease) and reactor pressure (pressure will stop increasing or will
start to decrease).
 Co-catalyst (AT): Total co-catalyst feed will include flows on account of makeup for
already exhausted co-catalyst (AT), moisture, other impurities & normal flow
required in ideal condition. Signs of improvement in reaction should start to appear
after this make-up. Improvement in reaction will be indicated by (C2% in PGC
reading, it should become steady or start to decrease) and reactor pressure.
 Catalyst (PZ): During first 2 hrs when make-up of co-catalyst is being done, some
extra PZ flow should also be maintained in addition to normal flow. This extra PZ
feeding amount should be in proportion to extra co-catalyst that is being fed on
account of make-up of already exhausted co-catalyst only.

b) Normalizing reaction conditions

Extra catalyst and co-catalyst feeding need to be continued further for next 2-3 hrs for
bringing back PGC parameters, mainly ethylene, in normal condition as ethylene (C2%) had
increased & it has to be brought down.

Its DCS panel operator’s decision that at what pace reaction parameters will be brought back
without disturbing other parameters (temperature, pressure etc. in reactors).

 Co-catalyst (AT): For next 2-3 hrs co-catalyst in feed will be on account of moisture
and other undesired components, if they still persist, in addition to normal flow as
per ideal condition as well as some extra amount based on panel operator’s decision
as explained above.
 Catalyst (PZ): During this next 2-3 hrs Extra PZ flow should also be maintained in
addition to normal flow. Extra PZ feed here will be in proportion to the extra co-
catalyst (Fe) that is being fed to that bring back reaction parameters under range.

c) When reaction seems under complete control then total catalyst and co-catalyst, mainly
co-catalyst in this case, feed will be on account of moisture and other undesired components,
if they still persist, in addition to normal flow as per ideal condition.
d) During all these actions all other actions should also be taken that are needed to increase
MFR like increasing H2 % in 1st reactor.
4) Analysis- a case study:

On 14-01-2018, abnormal reaction condition controlled using this calculated co-catalyst flow.
After analyzing the reaction conditions it was ascertained that this abnormality in reaction is
being caused due to joint effect of Acetylene (trend attached on next page), moisture (26 ppm
as per lab result).

Reaction conditions:
Plant load =12 tph
DC I ratio = 60 %
DC II ratio =85 %

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Acetylene =1.5 – 3 ppm (follow acetylene trend)
Moisture with Hexane = 26 ppm (Hexane Dryer outlet as provided by Lab)
PZ batch = 8 mmol/lit of Hexane
AT batch concentration = 200 mmol/lit of Hexane
Slurry concentration: 400 gm/lit hx in R1 and 350 gm/lit hx in R2

TEAL FLOW PLANT LOAD: PLANT LOAD: PLANT LOAD:

12TPH 13TPH 14TPH
fN (kg/hr) 24.2 26.23 28.23
fM (kg/hr) 21.84 23.66 25.5
fI (kg/hr) 5 5.4 5.83
fMO (kg) 48

Appropriate CO-CATALYST feeding into RB 201

TIME fMO (kg/hr) fN fM fI Extra TOTAL Plant
LINE (Total: 48 (kg/hr) (kg/hr) (kg/hr) feeding to Feed load
kg to be bring C2% (F)(kg/hr) (tph)
fed) under range
Fe (kg/hr)
1st hour 18 25 22 5 - 70 12
2nd hour 30 25 22 5 - 82 12
3rd hour - 25 22 5 20 80 12
4th hour - 27 24 5.5 20 80 13
5th hour - 29 25.5 6 10 75 14

3.1) Steps followed:

I. During first 2 hours, total TEAL flow included flows on account of make-up for
already exhausted co-catalyst (fMO), moisture (fM ), other impurities, acetylene in this
case, (fI) & normal flow (fN) required in ideal condition. Total make up amount of co-
catalyst can be disturbed over period of 1hr or 2hrs. During this period feeding of
main catalyst (PZ) was also kept higher side than normal flow.
Signs of improvement in reaction started to appear after this make-up. Improvement
in reaction was indicated by (C2% in PGC reading started to decrease) and reactor
pressure (stopped increasing)
II. Extra co-catalyst feeding need to be continued further for bringing back PGC
parameters, mainly ethylene in normal condition as ethylene C2% had increased & it
has to be brought down. Total co-catalyst feeding included normal flow (fN), moisture
(fM ), other impurities, acetylene in this case, (fI) and (Fe). During this period, extra
catalyst (PZ) feeding in addition to normal flow was also kept in higher side.
III. When reaction seemed under complete control then total catalyst and co-catalyst,
mainly co-catalyst in this case, feed was on account of moisture and other undesired
components, as they still persisted, in addition to normal flow as per ideal condition.
IV. During all these actions all other actions like increasing H2 % in 1st reactor were also
taken.

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Acetylene quantity (ppm) slipping in with ethylene feed into Reactors on 14-01-2018 Remark

 This Acetylene trend shows that

continuously more than 1.5 ppm
acetylene was slipping in into the
reactors with ethylene feed.
 As per Mitsui, acetylene into the
feed should not be greater than 0.2
ppm for normal reaction and 2.0
ppm is the maximum allowable
concentration of acetylene.

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Lab Report 14-01-2018 Description

Reaction conditions:

 Reactor conditions were very similar to conditions explained

for undesired materials which cause deactivation of catalysts.
This condition led to sharp decrease in Reactor 1 and Reactor
2 MFR which further led to decrease in pellet MFR.
 Reactor 1 MFR decreased from 725 at 09:30 hrs to 143 at
15:30 hrs.

Actions taken:

 All actions were taken that should be taken to increase pellet

MFR.
 Calculated TEAL (AT) feeding appropriate for this kind of
situation started at 14:00 hrs.
 Once conditions improved AT flow slowly reduced without
disturbing reaction condition.
 PZ flow was also kept at slightly higher than normal level.

Result:

 Reaction conditions started to improve from 16:30 hrs after

increasing AT feeding it caused [AT/PZ] ratio to increase to
a level that must have been needed for that condition.
 ON-SPEC production achieved at 18:30 hrs.
 Reaction SHUT DOWN avoided.

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 5. Results and Conclusion

Mathematically calculated, based on theoretical studies, appropriate TEAL flow as per

situation resulted in improvement in reaction as expected after 2 hours as make up for already
exhausted catalyst and co-catalyst was done in first 2 hours along with excess flow on
account of moisture content and undesired component, acetylene in this case. Further, excess
feeding of catalyst and co-catalyst for another 3 hours brought back PGC parameters,
Ethylene % in gaseous phase in reactors in this case, and pressure in both reactor in range as
prescribed.

Based on [AT/PZ] ratio as prescribed for different grades, it became clear that reaction for
grades having low [AT/PZ] are more vulnerable to disturbance because of such undesired
components as compared to grades having high [AT/PZ] ratio. Therefore, [AT/PZ] ratio can
be kept high (optimized) for grades that have low [AT/PZ]. For example, as we have [AT/PZ]
ratio 5.9 for FILM grade, it can be increased to 9.5 - 10 for better outcome in context of
reaction disturbances and reducing main catalyst (PZ) consumption.

6. Recommendations:
i) Early detection of slipping in of undesired component will be helpful in taking
timely action which will not only prevent reaction from being abnormal but also
prime grade production can be ensured. Therefore, it will be better to make PGC
data available for Acetylene on DCS.
ii) Increasing [AT/PZ] ratio for FILM grade to 9.5 - 10 from 5.9 for better outcome
in context of reaction disturbances and reducing main catalyst (PZ) consumption.
iii) For controlling moisture, increase in temperature profile of Hexane Dehydrator
can be considered by 3- 4 0C by increasing steam flow into Dehydrator bottom
Reboiler as at steady state it will result in decreasing of moisture content in
outgoing Hexane. In fact, this has resulted in decreasing moisture content in
outgoing Hexane.
iv) Reaction conditions should be kept as per recipe provided by Mitsui for different
grades like keeping DC1 and DC 2 ratios near prescribed value etc.
v) Care should be taken while analysing such conditions and calculating excess
TEAL flow needed to counter such issues because unused active co-catalyst may
cause some problems like:
a) Unused active TEAL flow to Waste Hexane Recovery section may lead to
plugging of pores of molecular sieve material present in Hexane Dryer as size of
TEAL molecules are very similar to pore sizes of molecular sieve material (S.
Mitra, 2012).
b) In some cases chances of fire may occur in LP Pit area.
c) After an optimal value of [AT/PZ] ratio, productivity decreases due to over
reduction of Ti3+ to the inactive Ti2+ form (Suba, Arva and Nemeth, 2007).

13
7. References
1) “Aluminum Compounds, Organic” in Ullmann's Encyclopedia of Industrial
Chemistry, Michael J. Krause, Frank Orlandi, Alfred T. Saurage, Joseph R. Zietz Jr.
2002, Wiley-VCH, Weinheim.
2) https://ir.nctu.edu.tw/bitstream/11536/24456/1/000335876100006.pdf
3) http://research.cm.utexas.edu/nbauld/polymers.htm
4) Olefin Metathesis and Metathesis Polymerization, By K. J. Ivin, J. C. Mol.
5) Handbook of Polymer Synthesis: Part B (In Two Parts), By Hans R. Kricheldorf
6) Catalytic Polymerization of Cycloolefins. Ionic, Ziegler-Natta and Ring-Opening
Metathesis Polymerization by By V. Dragutan and R. Streck.
7) Metal Catalysed Acetylene Oligomerisation, School of Chemistry, University of
Tasmania, Samuel Stefan Karpiniec, September 2010.
8) The effect of a Zeigler Natta catalyst and the polymerization parameters on the basic
properties of polyethylene, P. Suba, P. Arva, S. Nemeth, Hungarian journal of
industrial chemistry, 2007.
9) Revisiting the Aufbau Reaction with Acetylene: Further Insights from Experiment
and Theory, Samuel S. Karpiniec†, David S. McGuinness*†, Michael G. Gardiner†,
Brian F. Yates†, and Jim Patel‡, School of Chemistry, University of Tasmania,
Private Bag 75, Hobart 7001, Australia.
10) https://pubchem.ncbi.nlm.nih.gov/compound/triethylaluminum#section=Reactivity-
Alerts
11) Handling chemicals safely, by Nederlandse Vereniging, van Veiligheidstechnici,
1980, Netherland
12) Control moisture problems in slurry-based polyolefin operations, S. MITRA,
University of Newcastle, New South Wales, Australia, 2012.

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