Professional Documents
Culture Documents
2011
Content
HDPE, MDPE and LLDPE linear polyethylenes Application History Catalysts HDPE processes Process control Process safety Key equipment Investment cost Cost of production
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HDPE, MDPE, LLDPE: LLDPE: linear polyethylenes Classification by density determined by short chain branching through comonomer content
No of S CB
LLDP E
M D PE HD PE
0,91 5
0,926
0,940
0,970
Properties
Melt index 0,03 - >100 g/10 min (190 C/2,16 kg) Melting point 120120-140 C Polydispersity (TVK grades) grades)
Monomodal Bimodal
6-8 1010-20
Application
HDPE/MDPE
LLDPE
Extrusion coating 6% Injection moulding 5%
Other 12%
Film 77%
Application by Properties
100
Narrow MWD Medium MWD Broad MWD
10
min) ) MFR (g/10 min
LLDPE INJECTION MOULDING MDPE ROTOMOULDING LLDPE BLOWN & CAST FILM
0,1
0,01 0,890
0,900
0,910
0,920
0,930
0,940
0,950
0,960
Density (g/cc)
0,970 5
History
HDPE discovered in 1951 by P. Hogan and R. Banks Mid 1950s: commercial HDPE production in slurry process (Hoechst) and solution process (Phillips Petroleum) 1961: slurry loop reactor technology by Phillips Petroleum 1968: first gas phase process by Union Carbide Mid 1970s: first LLDPE process by Union Carbide Various processes available up to 400 kt/y capacity Global consumption, 2009
HDPE/MDPE LLDPE
1986: Phillips slurry loop process 140 kt/y, debottlenecked to 190 190 kt/y 2004: Mitsui slurry, cascade reactor technology 200 kt/y
Catalysts
Chromium
Silica supported hexavalent Cr Activation at high temperature before use Cocatalyst not necessary Medium to broad molecular weight distribution MgCl2 supported TiCl4 Metal alkyl cocatalyst necessary Narrow molecular weight distribution Preferred for bimodal products in cascade reactor technology very broad MWD Still developing Cocatalyst necessary Very narrow molecular weight distribution Bimodal capability in single reactor technology
Ziegler(-Natta)
LLDPE
8
10
Swing technology: LLDPE HDPE capability Simple process design Low investment and operating cost Bimodal capability with two reactors
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Solution Process
12
Solution Processes
Characteristics
Broad product range: LLDPE HDPE Bimodal capability with cascade reactors Higher investment and operating cost
13
14
Flash separation
8585-105 C; 42 bar 3-6 % ethylene concentration Isobutane diluent Heat removed by coolant in reactor jacket very good surface/volume ratio 10 bar; 80 C
Degassing
85 C; 0,1 bar
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Loop Reactor
C ataly st
Flash Tank
Purge Column
Powder silo
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Additive blender
Dewatering screen
Main feeder
Rotary feeder
Premix feeder Pellet water tank CIM Air blower Extruder Pellet water pump
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Slurry Process
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19
6-8 bar, 7070-90 C Overhead condensators Slurry coolers Reactor jacket Different molecular weight polymer in 1st and 2nd reactor Comonomer built into high molecular weight polymer
Diluent and polymer separation by centrifuge Diluent cleaning for low polymer removal
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10
Process Control
Melt index
Process Safety
Emergency kill to prevent reaction runaway except for CSRT Action valves automatically operated by predefined process parameters to separate/blowseparate/blow-down equipment Pressure safety valves, blowblow-down valves release to closed system, connected to Flare to burn blown hydrocarbon
Double mechanical seal on pumps in liquefied gas service Gas detectors Fire fighting system
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11
Key Equipment
Reactors
Loop with axial circulating pump Gas phase
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Reactors
Loop reactors
Long jacketed pipe straight vertical sections interconnected by elbows at top and bottom Built in axial pump to circulate slurry Good surface to volume ratio easy reaction heat removal
Vertical pressure vessel with increased top section to reduce polymer carry over Long residence time Reaction heat removed by external heat exchanger in recycle gas stream Difficult reaction control
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12
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Decanter Centrifuge
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13
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CMP Elements
28
14
Mixing in CMP
29
Investment Cost
Basis: WE 2010 Q1
Process Capacity Investment, million EUR ISBL OSBL Other project costs Total investment Specific investment cost, EUR/t LLDPE HDPE Gas phase Gas phase 325 300 98 49 53 200 615 94 47 50 191 637 HDPE Slurry 300 88 44 48 180 600
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15
Cost of Production
Basis: WE 2010 Q1
EUR/t
LLDPE HDPE HDPE Gas phase Gas phase Slurry 851,8 927,8 927,8 96,2 19,9 19,9 17,9 967,9 947,7 945,7 28,9 7 35,9 17,1 13,7 30,8 1034,6 26,9 8,4 35,3 15,8 14,7 30,5 1013,5 29 13,5 42,5 18,2 14,2 32,4 1020,6
Total raw materials Total utilities Total fixed costs
Ethylene Comonomer Catalysts&chemicals Total raw materials Power Other utilities Steam credit Total utilities Direct fix costs Allocated fix costs Total fixed costs Total cash costs
100% 90% 80% 70% 60% 50% 40% 325 kt Gas phase LLDPE 300 kt Gas phase HDPE 300 kt Slurry HDPE
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Spring
16
33
34
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