RETROFIT OF AUTOCLAVE REACTORS FOR THE PRODUCTION OF

HDPE TO VLDPE

LLOYD w.

PEBSWORTH

SENIOR PRINCIPAL ENGINEER

PROCESS RESEARCH
AND

DEVELOPMENT
COMPANY

uSI CHEMICALS

Prepared for presentation at the 1987 annual AIChE Meeting November 15-20, 1987 Recent Process Developmens in Olefin Polymerization

INTRODUCTION

Production of polyethylene in high pressure stirred Reports autoclaves using Ziegler type catalyst is not new. A of this type synthesis date back as Far as two decades. renewed interest in improving the versatility of existing autoclave systems has occurred with the commercialization of fluidized bed LLDPE production. This is evidenced by the increasing number of patents issued in this area and by the recent commercial production and licensing activities.
The

encroachment of

LLDPE

in many

traditional

LDPE

markets

displacement of many products. In the past cyclic demands accentuated by periodic overcapacity of various types of polyethylenes has shown a need for a "universal" process that could provide "swing" capabilities. Conversion of existing autoclave reactors to swing units can relieve these problems. The purpose of this paper is to give a brief summary of the results of retrofitting an existing commercial scale autoclave polyethylene reaction system for the production of a universal range of polyethylene homopolymers and copolymers. Retrofit systems generally use coordination metal catalysts
has
in slow growth
and even

resulted

and

1-olefin

comonomers to produce polymers with

0.9M

densities

in

the range of 0.92 g./c.c. to

g./c.c.

The

system

described

here

capability
0.87

of producing

polymers

has a demonstrated with product densities from

g./c.c.

to 0.96
from

g./c.c.

polyethylene range
products.

This spans the entire high density to very low density

PROCESS DESCRIPTION

basic changes needed for retrofit operation. Note that the compression, reaction, recycle, and product collection steps remain basically the
Figure
1

summarizes

the

same.
The

catalyst system

has
The

been modified to

permit injection

of

catalyst slurry.
is necessary

necessary to prevent
system

addition of circulating pumps is catalyst dilution catalyst settling.

A

to

provide

the

proper

concentration of

catalyst.
will depend on the settling rate of the catalyst. Catalyst particle size and thevpresence or absence of prepolymerization are important factors in selecting circulation rate.` Centrifical pumps with mechanical seals and The seal flush have proven to be adequate for this Job. dilution is varied depending on catalyst activity, catalyst
Circulation rate

capacity. The same positive displacement pumps used in free radical polymerization are used here. The cocatalyst system utilizes the existing injection pumps and feed tanks. The system is designed to
demand,
and

injection

provide precontact of the catalyst with cocatalyst if necessary otherwise the cocatalyst is injected directly to the reactor. A deactivation system is needed to avoid post reaction.

It should be noted that deactivation is conducted in the last reactor zone where stirring is utilized to disperse the deactivator. Further mixing occurs during pressure letdown. The deactivator which also acts as a neutralizer is fed to

Care is taken in suspension. the deactivator storage tank to exclude all oxygen by inert gas Addition of a positive displacement purge and padding. pump was necessary to accomplish deactivator addition. are done Data collection, and process calculations

the reactor

as

collodial

computer used has an The computerized system. industrially proven set of real-time system software. The data acquisition hardware is accessed from the ANSI/IEEE-583 Standard for Computer Automated measurement and control This permitted in-house development of software in (CAMAC). A total of 215 points were monitored. In-process FQRTRAN.

using

calculations performed
A

by

the computer are

listed in Figure
A

2.

system for metering hydrogen to the low pressure recycle

system is needed for melt index control. column is needed to assure that mineral

simple

spirits,

drying used for

catalyst dilution
The

and system

flushing is free of moisture.

existing gas chromatographs were converted to measure The comonomer, diluent and hydrogen in the reactor feed. existing analog controllers with minor modifications were used existing modifier pumps were used The for process control. for comonomer injection.
Additional control of temperature and fresh feed addition point in the flash _gas compresson system was needed to
minimize comonomer knockout.

Facilities for
necessary if product

the addition of

an

inert diluent

are

is to be densitiy below 0.923 g./c.c. made without excessive comomomer knockout in the low pressure C2 fractionator an existing recycle system. Ethane from
U

ethane/propane cracking unit was used. The need for this system will be detailed later. A high pressure recycle adsorber has been added to the The system to scavenge poisons from the system. entire reactor feed is treated by routing the primary compressor discharge to upstream of the adsorbtion vessel which is located in the high pressure recycle system. System "dry out" is rapid at a total system recycle every six minutes. A combination adsorber bed of 13X molecular sieves and activated alumina is currently used. A more complete description of the process may be found in U.S. Patent No. 4,558,105.
bottom
in
an
SYSTEM CAPABILITIES

Product Density Product density is

when

controlled

by

adding butene-1

comonomer

desired product density is in the range of 0.925 to 0.926 g./c.c. When the desired product density is in the range of 0.87 to 0.925 g./c.c. ethane is added to the reaction system inlorder to change the butene to ethylene ratio. The resulting
the

with this ratio and with the incorporation characteristics of the specific catalyst. This relationship for three catalyst types is given in Figure 3. The use of ethane as diluent lowers the dew point of the

product density

varies

flash

loss of butene in this system. The use of ethane also lowers the density of the suction feed to the secondary compression system and therefore
gas feed and thus avoids knockout

or

avoids over pressure of the compressor first stage discharge. Figure 4 illustrates the effect of ethane addition on product density. The maximum density achieved was 0.960 g./c.c. This density value indicates the presence of a short chain branching level higher than that observed in solution and slurry produced HDPE. The cause for this higher branching frequency has not been firmly established. Dimerization of ethylene to butene-1 in the presence of hydrogen was shown to be the cause in one case. Some free radical polymerization is also suspected.
,

Melt Index

adjusting the level of hydrogen in the system. Melt index is also influenced by the reaction temperature and of course the catalyst type.
by

Typically melt index is controlled

Figure

illustrates

the temperature melt

index

relationship

for three catalysts.

Restrictions to stay below the stintering temperature, imposed on fluidized bed systems, does not exist for the retrofit system. As a result there is virtually no reactor restrictions on the production of low viscosity, low density products. Wide viscosity transitions can be made
in

very

short times.
1

For example the

product melt index has

one hour.

been changed from

to

35

in

less than

Reactor

fouling is not a_problem.

Deactivation and Neutralization Deactivatlon and neutralization is accomplished ln one step within the reactor. The last zone of a three zone reactor Stirring in the deactivation zone is utilized for this step. utilizes a turbine type mixer to disperse the deactivating and

neutralizing agent. Deactivation is accomplished by injecting a collodial suspension on a Hydrotalcite like material in mineral spirits.
Deactlvation occurs in the following manner:
Mgu.5A1.12<oH>13co3
H20 + Hcx.

---- >

Mg4.5AI..l2(OH)13Cl2

51120 +

co;

present in the Hydrotalcite first reacts with the chloride containing catalyst to produce HCI. Deactivation is achieved in this step. The.released HCl exchanges with water and CO2 of the Hydrotalcite to produce a chloride containing insoluble salt which is stable up to a temperature of 842F (723K). Neutralization occurs in this
The

water

second step.

advantages over alkaline earth metal salts in that the product of neutralization and deactivation is undesirable stable and therefore will not contribute to is limited by System corrosion downstream reactions. neutralization immedlately following the reaction step. Details of this method of deactivation are covered in U.S.

Hydrotalcite has

Patent

4,634,744.

Product Quality

Conventional

LLDPE made on

the

retrofitted autoclave

has

superior optical properties to that of LLDPE made on the fluidized bed reactors. Tests to date indicate that the autoclave products are less heterogenous and therefore have improved optical properties. Figure 6 compares film grade products made via autoclave, fluidized bed, and a solution
process.
Absence

of

solid catalyst support

in combination

with

catalyst activity results in a clean high density product which is free from silica nucleated gels which are often a problem in slurry and fluidized bed processes.
high
Swing Capacity

With
LLDPE

this system it is possible

VLDPE

to

transition

from

HDPE

to

matter of hours. Transition back to conventional LDPE production has been achieved in less than 24 hours. With additional equipment modification this can be reduced even further.
in
a
PROCESS ECONOMICS

to

Retrofit Costs
The

capital

investment

needed

for

retrofit

of

an

autoclave reactor is substantially less than that needed for the construction of a new gas phase unit. Conversion of the synthesis train is projected to take 10 to 15 million U.S.dollars. This cost will vary depending on sophistication of the product handling system and the feed stock
8

existing

.2

treating system. The ability to handle VLDPE downstream of Feed stock quality the reactor _requires special equipment. will determineithe extent of special equipment needed for feed Both of these variables are also factors in treatment. installing a gas phase process. The ability to use cocatalyst as
a

scavenger permits operation of the

monomer.

retrofit process

with lower

quality

Power Requirements
Much ado has been made

about the lower power requirements of

the gas phase process

as

compared

to the autoclave process.

This needs to be put in prospective.

First unit utilization

and

value added for the products made play a much more important Power costs partvin unit profitability than power costs. must be considered from several different prospectives. Total electrical power requirements forran autoclave reactor in conventional production breaks down to about 2 cents per pound of product at a conversion rate of about 13$ of the This compares with a cost monomer per pass through the reactor. of about 1.1 cents per pound for fluidized bed production. It has been demonstrated that the retrofitted autoclave can
operate

acceptable product at a pressure of Operation at this lower pressure will result 12000 psig. This will in a decrease of power costs of about 25%. reduce the power requirements to about 1.5 cents per pound. The conversion rate for the autoclave can be increased by lowering the feed gas temperature utilizing waste heat recovery refrigeration unit. in combination with an adsorbtion
and produce

Lowering

of

the

feed

gas temperature

from 100F (311K) to

will result ln an increase in conversion of about 1,21 per pass. This represents an additional savings in compression cost of about 91. The total power costs would be At this reduced to about 1.3 cents per pound of product. point the lower costs of pelletizing a molten stream versus a particle stream will bring the costs to near equality.
70F (29MK)
Time

for Conversion
The

conversion of the reaction system can be made with a minimum of process interruption. With proper planning most equipment can be installed without interruption of the conventional process. Down time for tie-ins has been demonstrated to be about three weeks. Installation of special product handling equipment will take longer. Conventional hot melt handling equipment can process retrofit product in the density range of 0.960 to 0.900 g./c.c. without modification
provided sufficient extruder power is available.

fluidized bed system will result in a very rapid rise in power requirements due to the required low conversion rates. This is due to the fact that the reactor temperature must be maintained below the stintering temperature of the product being synthesized if reactor
Production of
VLDPE

in

fouling is to be avoided. Figure 7 illustrates the magnitude of this problem. It should be noted that at a product density of 0.880 g./c.c. the softening point of the polymer is below 3220K or 120F. It is estimated that a production rate cut of more than 50% will be needed if reactor fouling in a fluidized bed is to be avoided. In VLDPE production the
10

retrofitted autoclave is the more efficient user of power. For the retrofitted autoclave the only limitation will be the melt index/temperature relationship of the catalyst.
DEVELOPMENT POTENTIAL

Tailoring of the Nata Ziegler catalysts for operation at higher pressure and temperature is still much in the development stage. With the flexibility of this type catalyst considerable progress can be expected in improving reactivity, comonomer selectivity, and temperature/polymer molecular weight

relationships.

-Development of

catalyst

which permits uniform

incorporation of propylene along the polymer chain is expected to give a product with superior properties. This development would result in a substantial decrease in production cost if propylene could be substituted for butene-1 as comonomer. Useqof reactor temperature zoning in conventional LDPE production is well established. Application of these techniques to retrofit production isqsure to lead to a very versatile system. low temperature in one zone and high By operating at temperature in the second zone products with a bimodal Use of molecular weight distribution can be produced. different selective catalysts in each zone can enhance these

differences.

temperature profiling to improve long conversion rate while maintaining product viscosity, used in conventional polymerization, may well be used to enhance productivity, improve film grade optical properties, and
Use

of

reaction

to improve ease of processing.

ll

,-- e
with very low Control of oligomers, a potential problem achieved in the retrofitted density polymers, is more easily First variation of high pressure recycle separation system. of will result in some control of the amount conditions Since the product enters in the product.
oligomers remaining

the

low

pressure separator
of

application
accomplished.
Lower

devolitizing

system as a liquid the equipment is more easily

pressure reactor operation in combination with

reinjection of the comonomer would permit the use hand higher pressure of higher 1-olefin comonomers. On the other melt index/temperature and can enhance the activity
knockout and

relationship

of some

potential advantages of

Figure 8 summarizes the catalysts. a retrofitted autoclave system.

12

\ 212
*

LEGENDgFOR FIGURE

10 12
1M

16

20

21a 216
22

22a 22b 23a 23h 23c

2M

2Ua 24D

25a
25D

26 27 29
32

32a 32b 32c 336 33b 330

3Na

34b
3&c

35 36 37 40 42
43

44 46 50
51 53
5M

58 60 62 64 66 70
72

Catalyst Mix Tank Catalyst Circulation Pump Deactivator Injection Pump Catalyst Injection Pump Cocatalyst Feed Tank Cocatalyst Injection Pump Cocatalyst Injection Pump Deactivator Feed Tank Deactivator Injection Pump Product Cooler High Pressure Separator First High Pressure Recycle Cooler Second High Pressure Recycle Cooler First High Pressure Recycle Knockout Pot Third High Pressure Recycle Cooler Second High Pressure Recycle Knockout Pot Fourth High Pressure Recycle Cooler
Adsorber Adsorber Discharge

Reactor Reactor Top Zone Reactor Middle Zone Reactor Bottom Zone Makeup Ethylene Supply Line First Stage Primary Suction Drum Second Stage Primary Suction Drum Primary Compressor First Stage Primary Compression Second Stage Primary Compression Primary Compressor Kickback Cooler First Stage Primary Discharge Cooler Second Stage Primary Discharge Cooler Secondary or Hyper Compressor First Stage Secondary Compression Second Stage Secondary Compression First Stage Secondary Discharge Cooler Second Stage Secondary Discharge Cooler Comonomer Injection Line Secondary Compressor to Reactor Feed Line Ratio Modifier Injection Line Flash Gas Compressor First Stage Flash Gas Compression Second Stage Flash Gas Compression Third Stage Flash Gas Compression First Stage Flash Gas Knockout Pot Second Stage Flash Gas Knockout Pot Third Stage Flash Gas Knockout Pot First Stage Flash Gas Cooler Second STage Flash Gas Cooler Third Stage Flash Gas Cooler Hydrogen Injection Line

74

Filter

Legend for Figure

76 78 80
83

Continued
Adsorber Discharge
LPS LPS

Deactivator Circulation Low Pressure Separator

Filter
Pump

82
85

86

Product Extruder/Pelletizer Pellet Spin Drier

Off Gas Knockout Pot Off Gas Cooler

FIGURE 2

DATA COLLECTION

VIA COMPUTER

REAL TIME SYSTEM

ANSI/IEEE-583

STANDARD

CAMAC

215

DATA

POINTS

HO

ALARM

POINTS

TREND DISPLAY AND GRAPHING

INPROCESS CALCULATIONS
CATALYST

PRODUCTIVITY
RATE

CATALYST ADDITION

COCATALYST ADDITION RATE

DEACTIVATOR ADDITION RATE

NORMALIZED
COMDNOMER
TO

G. C. OUTPUT
MONOMER

RATIO

SET POINT

FOR COCATALYST FOR

INJECTION RATE

SET POINT

DEACTIVATOR RATE
ENERGY

EXTRUDER

SPECIFIC

PRODUCTION RATE

FIGURE

960

950

940

930

920

910
C.C.

900

890
C B

aeo`

0{5

1.0

1.5

2.0

'2.5

Average Molar Ratio, Butene-l/Ethylene

FIGURE 4
ETHANE VS. PRODUCT DENSITY

960

BUTENE/ETHYLENE

950

940

930

920

910

900

BUTENE/ETHYLENE/ETHANE

890

880
I

'TI
1.0

1.4

1.2

0.8
WT. RATIO,

I 6.6
BUTENE/ETHYLENE

I
o 2

-I
0

'o.4

FIGURE 5

10
9 8 7 6

5 4

'_v

I/

Cf

__

iff

'_v

I I ff'

QE

8|7|5

6`rF-

r-

.1

0.910

g./c.c.
410 (483) 420
<4B9>

_I
360 (455)

L _.I
380
<4ee>
OF

L
390 (472)
(OK)

370
<4@1>

400

(478)

FIGURE 6

TETRQEITTE

EEEIDIZED

ESEETQN

HAZE

GLOSS

CLARITY
FILM INDEX*
IMPACT STRENGTH

PUNCTURE

IMPACT STRENGTH
TEAR

PROCESSING

*LACK OF

FILM IMPERFECTIONS

OR

GELS

FIGURE 7

260 (400)

I"

I
C
A

240 (389)

T
S
O

220 (378)

F
T
E

200 (366)

I
N G

180 (355)

Y?

o
I
N

160 (344)

OF

K)

140 (333)

120 (322)

100 (311)

_.I
.95 .94 .93 .92
POLYMER

_L
89

.91

90

88

DENSITY,

g./c.c

FIGURE 8

ADVANTAGES OF RETROFITTED AUTQCLAVES

LOW

RETROFIT COST

SHORT CONVERSION TIME

EXCELLENT SWING CAPACITY

HDPE

LLDPE LDPE VLDPE

BEST VLDPE ECONOMICS

LOW

SYSTEM INVENTORY QUICK DRY OUTS LOW TRANSITION TIME

IN

SI.TU DEACTIVATION

AND NEUTRALIZATION SUPERIOR DEACTIVATOR

PRODUCTS WITH

NO

WIDE RANGE OF VISCOSITIES REACTOR FOULING PROBLEMS

MAY

BE MADE

THE REACTOR MAY BE ZONED AND TEMPERATURE PROFILED

CAN BE OPERATIED OVER A WIDE

TEMPERATURE AND PRESSURE RANGE

MULTIPLE CATALYSTS AND COCATALYSTS

GOOD QUALITY GEL PRODUCTS

MAY

BE

USED

LOW

GOOD

OPTICAL PROPERTIES
POWER
DRAW

LOWEST

REMELT FOR

PELLETIZATION AND ADDITIVE INCLUSION IS

NOT

REOUIRED