INTRODUCTION TO
PURIFICATION
• FEEDSTREAM OVERVIEW
• PURIFICATION REQUIREMENTS
OVERVIEW
• IMPURITIES AND THEIR EFFECTS
• IMPURITIES REMOVAL MECHANISM
FEEDSTREAM OVERVIEW
• ETHYLENE is the main raw material for
producing polyethylene
– ETHYLENE = C2H4
– B.P.= -185.3 OC
FEEDSTREAM OVERVIEW
• COMONOMER
• HEXENE OR BUTENE - is used as a
comonomer for branching the polymer chain
which directly affect the resin density
– HEXENE = C6H12
– B.P. = 63.5 oC
– BUTENE = C4H8
– B.P. = -6.3 OC
FEEDSTREAM OVERVIEW
• HYDROGEN - is generally used as a chain
terminating agent in the polymerization
reaction to control the length of the polymer
molecules or the Melt Index of the M
catalyzed resin
– HYDROGEN = H2
– B.P. = -252.7 O C
FEEDSTREAM OVERVIEW
• HEXANE - is used as an Induced
Condensing Agent.
– HEXANE = C6H14
– B.P. = 67.0 O C
FEEDSTREAM OVERVIEW
• NITROGEN - is used to carry into the
reactor and as purge gas to purge the
product for un-reacted hydrocarbon. It is
also used to purge equipment during
operation and for preparation of equipment
for maintenance.
– NITROGEN = N2
FEEDSTREAM OVERVIEW
• TEAL OR T2 - used as co-catalyst in the
reaction process when using UCAT A or
“M” catalyst.
– TEAL = (C2H5)3Al
– B.P. = 186 OC
FEEDSTREAM OVERVIEW
• PROPYLENE - main raw material in the
production of the polypropylene.
– PROPYLENE - C3H6
– B.P. = -169.2 OC
PURIFICATION
REQUIREMENTS OVERVIEW
• All reactor feed streams must be treated to
remove impurities, which have an adverse
effect on the catalyst. The purification
facilities for each feed stream may consist
of one or more operations each of which are
specific to the impurities which are being
removed.
PURIFICATION
REQUIREMENTS OVERVIEW
• Here at JGSPC, an Ethylene Purification
unit is consist of facilities for the removal
of Sulfur (S2), Carbon Monoxide(CO),
Oxygen(O2) and Water(H2O).
PURIFICATION
REQUIREMENTS OVERVIEW
• The comonomer Purification System is
consist of a Degassing Column to remove
Carbon Monoxide (CO); Carbon
Dioxide(CO2), Oxygen(O2) and molecular
sieve Dryer to remove trace amount of
Water or Moisture(H2O).
PURIFICATION
REQUIREMENTS OVERVIEW
• The Hydrogen feed stream goes to a
molecular sieve dryer to remove trace
amounts of water(H2O).
PURIFICATION
REQUIREMENTS OVERVIEW
• Nitrogen Purification unit consists of a
Deoxo Vessel to remove trace amounts of
Oxygen(O2) and then through a molecular
sieve Dryer to remove water(H2O).
PURIFICATION
REQUIREMENTS OVERVIEW
• Hexane Purification system is consist of a
Degassing Column to remove Carbon
Monoxide (CO), Carbon Dioxide(CO2),
Oxygen(O2) and molecular sieve Dryer to
remove trace amount of Water or
Moisture(H2O).
PURIFICATION
REQUIREMENTS OVERVIEW
• Propylene Purification unit is consist of a
Degassing Column to remove Carbon
Monoxide (CO), Carbon Dioxide(CO2),
Oxygen(O2); and other equipment for the
removal of Sulfur(S2), Methylacetylene/
Acetylene/Propadiene (MAP) and
molecular sieve Dryer to remove trace
amount of Water (H2O).
EFFECTS OF CONTAMINANTS
• DEACTIVATE REACTION CATALYST
– React with active catalyst sites
– Block polymerization sites
– Cause incorrect catalyst mixing proportion
• ALTER RESIN PROPERTIES
– Hinder comonomer incorporation
– Change polymer chain length and branching
EFFECTS OF CONTAMINANTS
• ALTER REACTION OPERATING
CONDITIONS
– Take blow-off to remove impurities
– Reduce temperature to maintain product
properties
– Reduce rates
• RAISE REACTANTS QUANTITIES
REQUIRED
EFFECTS OF CONTAMINANTS
– More components require more feed to the
reactor
• INCREASE RESIDUALS IN RESIN
– Ash content will increase
• CAUSE REACTOR CONTINUITY
PROBLEMS
– Will cause sheeting or chunking
EFFECTS OF CONTAMINANTS
• CHANGE SELECTIVITY AND
ACTIVITY OF PURIFICATION
CATALYST
– Normal components or impurity for which the
purification stage was designed may not be
removed due to presence of other impurities.
– Unwanted side reactions may cause catalyst to
become inactive
EFFECTS OF CONTAMINANTS
• CAUSE DECOMPOSITION OF RAW
MATERIALS
– Impurities may react with materials to form
waste product and further contamination
– Render materials useless
• CAUSE LOSSES OF RAW MATERIALS
– May need to run excessive column vents or
tails to remove unwanted contaminants
EFFECTS OF CONTAMINANTS
• CAUSE SAFETY PROBLEMS
– Impurities may react with purification catalyst
or raw materials and form hazardous by-
products (acetylides, polymers, oil)
IMPURITY EFFECTS ON UCAT- A
CATALYST REACTION
• CO is an effective kill gas for the catalyzed
reaction
• CO2 significantly reduces U-A catalyst
productivity
• O2, H2O, Acetylene (below 20 ppm) do not
poison U-A catalyst
• MWD of U-A polymerized resin is not
modified by impurities
• Slight, but unimportant decrease of MI was
observed with water and oxygen
IMPURITY EFFECTS ON UCAT- A
CATALYST REACTION
• In general, U-A catalyst is less affected by
feed stream impurities due to presence of
TEAL in the reactor
• Some impurities in very small quantities are
pro-static agents and may effect the stability
of the process by inducing more static
charge to resin particle, than are being
discharge
IMPURITIES REMOVAL
MECHANISM
• CHEMICAL ADSORPTION
– Impurity is adsorbed into a porous material bed
(catalyst) and becomes a third component that
stays in the porous material is covered with this
third compound, regeneration of the bed is
necessary. Example: Deoxo Beds
– Regeneration - the process of bringing up spent
catalyst to its active state. (Using heated
Nitrogen).
IMPURITIES REMOVAL
MECHANISM
• HYDROGENERATION
– Another phase of chemical adsorption, this process
consist of the adsorption of the impurity in the porous
bed, reaction with another component (H2) and de-
sorption of the product caused by this reaction.
Example: MAP Removal Bed where acetylene is
adsorbed in the palladium catalyst and while it is
adsorbed, it reacts with the hydrogen injected at the
inlet of the bed. The product of this reaction,ethylene
or ethane goes in the stream
IMPURITIES REMOVAL
MECHANISM
• PHYSICAL ADSORPTION
– Removes impurities based on size or polarity.
Example: Molecular sieves where water stays
adsorbed into the sieve and is de-sorbed during
the sieve regeneration. The sieve material does
not react nor catalyze any reaction so
regeneration is a physical process
FACTORS AFFECTING
ADSORPTION
• AREA EXPOSED
– Porosity
• VELOCITY
– Residence time
• CONCENTRATION
– Higher - Harder
• LENGTH OF REACTION ZONE(LRZ)
– Longer - Better
PROCESS
• FOR GAS STREAM (ETHYLENE)
– Heat up
– Sulfur removal - G72D Zinc Oxide adsorbent
– CO removal - G66B type 2130 zinc oxide
hydrogenation catalyst
– O2 removal - UCC1101 copper chromite on silicon
deoxide
– Dryer - UOP 13 XPG molecular sieve, sodium
alumino silicate
PROCESS
• FOR LIQUID STREAM (PROPYLENE)
– Degassing - distillation
– Cooling - prevent temperature runaway
– Sulfur removal - ALCOA Selexorb COS
– MAP removal - G68F
– Dryer - UOP 13 XPG
– Filter - particulate removal
POINTS OF CONCERN
• BED TEMPERATURE ALARMS
• BED TEMPERATURE ALARMS AND
MONITORING
• VESSEL PURGING AND CATALYST
DEACTIVATION
• VENTS
• INSULATION OF PROCESS EQUIPMENTS AND
LINES
• REGENERATION NITROGEN PIPING
CHEMICAL REACTION
• SULFUR REMOVAL
– H2S + ZnO ZnS + H20
– COS + ZnO ZnS + CO2
• CO REMOVAL
– CO + CuO CO2 + Cu
– CO + Cu2O CO2 + Cu
CHEMICAL REACTION
• O2 REMOVAL
– 2 Cu + 0.5 O2 Cu2O
– 2 Cu + O2 CuO
• C2 OXIDATION
– 6 Cu2O + C2H4 2 CO2 + H2O + 12 Cu
• COPPER ACETYLIDE REMOVAL
– CuC=CCU + H2 Cu + Hydrocarbon
PROPYLENE
• FEED SUPPLY
• PRESSURE 340 psig/2344kpag min.
350psig/2413kpag normal 370
psig/2551kpag max.
• TEMPERATURE -10 oC min. 30 oC
normal 40 oC max.
PROPYLENE
• DESIGN FLOWRATES
– 45,300 lb/hr / 20,548 kg/hr Normal
– 51,000 lb/hr / 23,170 kg/hr Maximum
• NORMAL OPERATING PRESSURE
– 305 psig / 2,100 kpag
– Column pressure controlled with a flow controller
on the steam to the reboiler
PROPYLENE
• FEEDSTREAM QUALITY
– IMPURITY MAX.ppmV FINAL PRODUCT
– CO2 5 <0.1
– CO 5 NIL
– O2 5 NIL
– H2O 5 <0.1
– S2 3ppmW 0.1
– Oxygenated HC including ALCOHOL
10 0.1
– MAP 10 <0.5
PROPYLENE
• DESIGN BASIS
– Distillation (Stripping) step for removal of CO2, CO,
and O2
• DESIGN OPERATION AND SAFETY
CONSIDERATION
– Turndown from 100% of the flow required for the
product with the maximum demand to 50 % of the
flow required for the product with the minimum
demand
PROPYLENE
• ADSORBENT(SULFUR REMOVAL)
– ALCOA SELEXSORB COS (Promoted
Activated Alumina)
• SAFETY CONSIDERATIONS
– Regeneration with hot nitrogen
– No preload
– 3-5 year bed life to replacement
– 18 hour regeneration time
PROPYLENE
• ADSORBENT(MAP REMOVAL)
– UNITED CATALYST G-68F (Palladium)
• SELECTIVITY
– METHYLACETYLENE, ETHYLENE,
PROPADIENE, PROPYLENE (EXCESS O2
WILL REACT WITH UNSATURATED
HYDROCARBONS)
PROPYLENE
• SAFETY CONSIDERATIONS
– Non-regenerable
– Sulfur and Arsine irreversible poisons to G-68F
Normal Sulfur and Arsine concentrations must be
kept less than 0.1 ppmw
– High temperature shutdown normally set at 50 oC
– 3-5 year bed replacement
– H2 feed to bed stops automatically on low propylene
flow
PROPYLENE
• ADSORBENT(DRYER)
– UNION CARBIDE 13 XPG Molecular sieves
• SAFETY CONSIDERATIONS
– Regeneration with hot Nitrogen
– Controlled preload with Propylene to prevent
temperature excursions
– 3-5 year bed life to replacement
– 7.5 hour regeneration time
ETHYLENE
• PRESSURE
– Low 2827 kpag
– High 3477 kpag
– High-High 3571 kpag
• DESIGN FLOW RATES
– Minimum 6,000 lb/hr ( 2,722 kg/hr)
– Normal11,572 lb/hr (25,458 kg/hr)
– Maximum 14,464 lb/hr (31,820 kg/hr)
ETHYLENE
• TEMPERATURE
– Minimum -24 oC
– Normal30 oC
– Maximum 150 oC
ETHYLENE
• EMERGENCY SHUTDOWN SYSTEM
(ESD)
– In the event of major emergencies such as fire
or gas release
– Temperature in the purification beds is high
(125oC), two thermocouples sustained for 2
minutes
ETHYLENE
• FEEDSTREAM PURIFICATION
• IMPURITY MAX. FINAL PROD.
– CO 0.2 <0.1
– O2 0.5 <0.1
– H2O 5.0 <0.1
– CH3OH 5.0 <0.1
– S2 AS H2S 0.2 <0.1
– CARBONYLS 0.1 <0.1 AS MEK
ETHYLENE
• SEQUENCE OF REMOVAL
– SULFUR (G72D, ZnO)
– CARBON MONOXIDE (G66B, CuO)
– OXYGEN (UCC 1101, CuCr)
– WATER, METHANOL, CARBONYLS (UOP
13XPG)
ETHYLENE
• EXTENDED SHUTDOWN
– 12 hours to 7 days, to be depressurized to 1000
kpag
– > 7 days, system to be depressurized and kept
under Nitrogen blanket
