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BENCH SCALE UNITS

AND PILOT PLANTS FOR


POLYOLEFINS
RESEARCH

POLYMERZATION
CHAIN GROWTH

STEP GROWTH

Unsaturated molecules

Chemical reaction between multifunctional


monomers molecules.

ADDITION

CONDENSATION

Reaction does not involve low


molecular byproduct formation.

FREE RADICAL
T, P activation

By-product formation. Polyurethanes


Polyamide (nylon); PET

COORDINATION
Coordination catalyst.

Polyethylene (PE); Polypropilene (PP);


Polyvinyl chloride (PVC); Polystyrene (PS)

ADDITION

IONIC

WIDE RANGE OF PROCESS AND PRODUCTS


PID Eng&Tech experience is focused on POLYOLEFINS
PRODUCTION: POLYETHYLENE AND POLYPROPYLENE
Other processes can be studied.

POLYOLEFINS PRODUCTION PROCESSES


HIGH PRESSURE
PROCESSES

LOW PRESSURE
PROCESSES

High temperature and pressure


600-3000 barg; 200-300C
LDPE

SLURRY
Gas monomer
Liquid solvent
Solid polymer
Reactors: CSTR, LOOP
70-110C
8-40 bar

Catalytic processes
(Coordination catalysts)

GAS
Gas monomer
Solid polymer
Reactors: CSTR, Fluidized bed
70-110C
20-25 bar

SOLUTION
Gas monomer
Liquid solvent
Diluted polymer
Reactors: CSTR
170-200C
90-100 bar

LABORATORY EQUIPMENT FOR POLYOLEFINS


RESEARCH
SLURRY PHASE

SEMI-BATCH
STIRRER TANK
REACTORS

CONTINUOUS
STIRRED TANK
REACTORS

Most common laboratory


scale installations.
Installations easy to operate.
Catalyst testing

One reactor o several reactors


in series.
No commercial installations.
Product development

PRODUCTS FABRICATED BY PID Eng&Tech

GAS PHASE

SEMI-BATCH
STIRRER TANK
REACTORS
Complex installations
because of stirring and heat
removal.
No commercial installations.
No PID Eng&Tech experience.

Elements in Slurry Phase Polyolefins Production


Main streams:

MONOMER: Ethylene; Propylene

HYDROGEN (control agent of the molecular


weigh of the polymer)

COMONOMERS: low molecular weight


olefins (ethylene, propylene, 1-butene; 1hexene)

SOLVENT: heptane; hexane; isobutane

CATALYST: supported coordination catalyst


(Ziegler-Natta; chromium oxide;
metallocene)

COCATALYST: catalyst activation and


scavenger (TEA, TIBA )

Raw Material Purification

Removing potential traces of water and oxygen


from fluid stream.

Pre-purified area comprises adsorption beds in


series for each feed line.

Typical adsorbents: activated alumina; molecular


sieve, etc.

Regeneration process: high temperature and


sweeping with an inert gas.

In situ regeneration system can be included.

Laboratory Scale Batch Units

SS316 stirred autoclave reactor 500 ml to 4 l


Heating jacked; cooling coil.
Maximum pressure: 50 bar
Maximum temperature: 100C
Continuous gas monomer, hydrogen and
comonomer feed lines.
Continuous liquid comonomer lines.
Solvent addition system.
Gas composition analysis system: MicroGC

Reactor Control Pressure.


Monomer feed line.

Monomer is added continuously during the reaction


to replenish the consumption for the polymer
formation.
Reactor pressure is controlled adjusting the gas
monomer addition.
Pressure regulation can be carried out by a manual
pressure regulator or through the mass flow controller
control valve.
Mass
flow
controller
measures
monomer
consumption.
In the case of polypropylene, polymerization can be
carried out in liquid monomer (Bulk Polymerization).
Pressure is established by the liquid-vapor equilibrium
of the propylene.

Comonomer feed lines.

Comonomers can be added like gases or liquids


according to the operation pressure and the
liquid-vapor equilibrium of the compound.

Hydrogen and gas comonomers flow are


measured and controlled by Mass Flow
Controllers. Heating tracing of the line is often
necessary to maintain the vapor phase.

Liquid comonomers can be added by a high


performance pump or by nitrogen pushing and
a liquid mass flow controller.

Vapor-Pressure Line for Propylene


T (F)

T (C)

P (barg)

35.6

59.0

15

140

60

26

Gas Phase Composition Control

Final product properties depend of the monomer,


hydrogen and comonomer concentration.

Hydrogen/monomer and comonomer/monomer


composition ratios in gas phase during the reaction can
be controlled.

Gas composition can be measured at nearly real time


(2-4 min of delay) by a MicroCG.

Result of this analysis can be integrated in the control


system. Hydrogen and commoner flows are modified
for keeping a constant composition in the reactor.

Batch Operations

Nitrogen and vacuum lines are used for system


inertization, pressure test and cleaning.

Solvent is loaded in batch mode before the


reaction. Addition can be carried out through a
pump or by nitrogen pushing from a graduated
burette.

Catalyst (solid) is loaded in the beginning of


the reaction sweeping it with the monomer.

Cocatalyst (solution) is injected to solvent


before reactor pressurization.

Laboratory Batch Units


Advantages and Requeriments

Polymerization reactions are complex processes.


Equipments easy to operate.
Procedures easy to standardize and validate.
Low investment, low waste of raw materials and
catalyst.
Catalyst productivity test.
Product properties screening: melting index; density;
comonomer incorporation.
Small quantities of polymer (< 250g). Limitations in
product analysis.
PID Eng&Tech has a widely experience in these
installations.

Pilot plant for continuous polyethylene production


at micro-scale
OBJECTIVES

MAIN CHALLENGES

Micro-scale industrial process


simulation.

Solid suspension transfer and flow


control systems:

200-500 g polymer/h

catalyst suspension;

Different reaction steps in series.


Bimodal products.

polymer suspension

Mechanical polymer properties


determination
Low raw material expenses and low
amount of residues generation in
relation with industrial Pilot Plant.

Changes in control strategy regards to


batch mode:
control of monomer consumption
in the units;
level control system
Continuous addition of solvent and
cocatalyst.

Process Description
Two reaction step with different operation
conditions (bimodal products):
Temperature
Pressure
Hydrogen/comonomers incorporation
Residence time (volume; solvent flow)
Flash step for solublized gas removal
between reaction step
Catalyst feeding to first reactor

The plant comprises:


Two 2 liters SS316 stirred autoclave reactors in series
Flash unit between reaction step
Raw material purification area
Continuous catalyst suspension addition system
Continuous cocatalyst solution feeding system
Monomer addition system with pressure control
Gas and liquid comonomers addition with gas phase composition control.
Solvent pumps
Two MicroCG for reactor gas phase analysis (one for each reactor)
Operating conditions
Maximum pressure 15 barg; operating pressure: 2-9 barg
Maximun temperature: 100C; operating temperature: 65-85C

Catalyst Addtion System


Catalyst suspension addition system for Micro Pilot Plant has to satisfy several requirements:
- accurate control of the quantity of catalyst fed,
- low flow ranges ( 0.1mg/min),
- avoiding blockage due to solid decantation,
- no inert gas addition to reactor,
- and precise control of catalyst flow independent of reactor conditions changes.

Configuration according to catalyst properties and


operation strategy.
Wide range of flow; independent of the process
conditions.
Validated system in operation conditions
Good performance in the presence of high diameter
catalyst particles and aggregations, with low mechanical
components abrasion.
Integration in ethylene consumption control loop

Polymer Suspension Transfer Systems


The instrumentation for slurry transference between unit is limited by:
Small flow ranges, 5-50ml/min (0.3-3 l/h)
Minimum diameter of pipes, valves or other elements to avoid solid blockage.
There is no comercial instrumentation for solid-liquid pumping at required flows.
Requirements for polymer slurry transference systems:
Pumping slurry against the unit pressure
Transferred volume must to keep the concentration (polymer/solvent ratio) of the reactor
Avoiding slurry sedimentations in the pipes and blockage of high size polymer particles.
Generating a nearly continuous slurry flow, avoiding process disturbances in process
conditions (pressure, level) due to transfer system.
Covering a wide range of working flows.
Allowing the integration with level control loops

Polymer Suspension Transfer Systems


Solid movement between reaction steps has been widely studied. Specific technology
has been develop for slurry transfer between units.

Transfer system behaviour


(reactor teorical concentration, 310 g PE/l C7)

Slurry concentration (gPE/l C7)

350
300
250
200
150
100
50
0
30

35

40

45

50

55

60

%vol

Agitation system 1

Agitation system 2

65

70

Control System
Temperature, pressure and composition ratio control systems are analogous to those used
in batch mode units.
Ratio Hydrogen/Ethylene R101
3.00
2.90
2.80
2.70
2.60
2.50
2.40
2.30
2.20
2.10
2.00
1.90
1.80
1.70
1.60
1.50
0

10

15

Reaction time (h)

20

25

Control System. Level Control.


Level measure in the units involves several limitations:
- Analogical measure is required
- Solvent is an hydrocarbon compound (hexane, heptane). No polar solvent.
- Polymer presence in the solvent (different slurry concentrations)
- Reactor size and connections
- Polymer growing over the walls of vessels and over inside elements.
- Variable temperature in the units
PID Eng&Techs capacitive level sensor is used in the three units. The sensibility and
the stability in this application is worse than in liquid-gas separator. Any case, it allows a
level control around 50-10% of the set point.

hydrocarbons

Control System. Ethylene consumption at reactors.


- Batch units: an established amount of catalyst is added and the response of the

system (monomer consumption) is study.


- Continuous units: the amount of polymer formed in each step must be controlled
in order to adjust percentage of the different polymer fractions in the final products.
Ethylene consumption R101 (Nml/min)

Strategies for monomer


consumption control (control
variable):
- Catalyst flow
- Residence time (solvent flow)
- Operation pressure

1500
1400
1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0
0

10

15

Reaction time (h)

20

25

Continuous Microscale Pilot Plant

Intermediate solution between traditional laboratory


research at laboratory scale and polyolefins industrial pilot
plants:
Low raw material cost compared with industrial
installations.
Operation in continuous and steady-state mode.
Bench-scale size
100-750 g/h
Scale-down continuous industrial system. The
development can be applied to different slurry
technologies (three reactors in series, etc.).
Main application: product development. Market demands
new specialized materials.
Production of enough amount of product for testing the
commercial relevance of it.

Thank you