경영」 9 -...
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서울대학교 「공학기술과 경영」 9강
1. 석유화학과 폴리올레핀
2. 폴리올레핀 (종류, 용도, 가공)
3. 폴리올레핀 제조공정
4. 올레핀 중합촉매
Ziegler-Natta 촉매
Metallocene 촉매
5. 한화토탈의 촉매개발 및 상업적용 사례
목 차
석유화학과 폴리올레핀
석유/납사 및 천연가스로부터 화학 기초유분을 생산하고, 이를 원료로 각종
중간 유도품과 합성수지(플라스틱), 합성섬유(폴리에스터, 나일론 등), 합성고무
등의 기초 화학소재를 생산하는 산업
석유화학산업?
우리나라의 석유화학 산업
세계 4위 생산규모(’14년)
- 국내 에틸렌 생산규모: 8.5 백만톤/년
- 세계 점유율: 1.9%(’90) → 5.3%(’14)
국내 제조업 중 4위 규모
- 생산액: 110조원
- 제조업 비중: 2.8% (’90) → 7.4%(’13)
국내 5위 수출품목
- 수출: 482 억불(총수출의 8.4%)
- 무역수지: 21억불 (’90) → 318억불(‘14)
*Source : 한국석유화학협회
Ethylene Capacity (2014)
세계 Polyolefin 산업
Major polymer 총수요(‘14): 2.24억톤
Polyolefins 수요: 1.43억톤 (62%)
- PP 5,800만톤, PE 8,500만톤
국내 Polyolefin 산업
총 생산능력: 930만톤/년
- PP : 8개사 424 만톤
- PE : 7개사 500만톤
한화토탈: 140만톤/년
- PP 3개 라인 70만톤
- PE 4개 라인, 70만톤
폴리올레핀 산업
폴리올레핀
1. 폴리올레핀 종류
2. 용도
3. 가공방법
Polyolefin의 종류
PE (polyethylene) • LDPE (low density PE)
• EVA (ethylene-vinylacetate copolymer)
• HDPE (high density PE)
• LLDPE (linear low density PE)
• UHMWPE (ultra-high molecular weight PE)
PP (polypropylene) • Homo-PP
• Random PP (propylene/ethylene)
• Ter-PP (propylene/ethylene/butene-1)
• Block PP (homo-PP+EPR)
Rubber/Elastomer • EPR (ethylene-propylene rubber)
• EPDM (ethylene-propylene-diene monomer)
• POE (polyolefin elastomer, ethylene/octene-1)
Specialty Polymer • PB-1 (polybutene-1)
• PMP (poly(4-methylepentene-1))
• COC (cyclic olefin copolymer, norbornene/ethylene)
LLDPE density 0.920~0.945 g/cc HDPE density 0.945~0.965 g/cc
LDPE density 0.915~0.925 g/cc
EVA VAM content : max 30wt%
Polyethylene (PE)
Isotactic PP
Syndiotactic PP
Atactic PP
Polypropylene (PP)
포화탄화수소 구조의 결정성 고분자
뛰어난 화학적 안정성
친환경적 (무독, 무취)
Recyclable
가격대비 우수한 물성
물성조절 용이 (분자량, 분자량분포, 공중합)
Melting temperature
HDPE: 130~135℃
PP : 160~165℃
PE, PP 소재의 특징
Amorphous Crystalline
High performance polymer
Basic polymer
Technical polymer
PA6/66
UHMWPE
PP
HDPE LDPE
PPS PA4,6
PBT/PET
POM
LCP
FP
PEK
PMMA
SAN PS
PVC
PPO
SMA ABS
PC
PES
PSU
PI
COC/COP
PEI
EVA
LLDPE
LDPE LLDPE/HDPE Iso-PP Syndio-PP
Density(g/cc) 0.915-0.935 0.915-0.965 0.91-0.92 0.89-0.91
Tm 95-120 ℃ 115-135℃ 160-165℃ 140-150℃
Tg -100 ℃ -100℃ -20℃ - 6℃
Young Modulus (GPa)
< 0.3 <1.0 1.4
Solvent resistance
medium high high medium
PP의 결정모양
PE, PP 수지의 용도
생활용품 식품용기/포장
의료용품
전기전자
건축/농업
자동차 경량화 (연비향상)
- PP 비중 0.92 g/cc
차체 중량의 10~15%는 plastics 소재,
그 중 절반이 폴리올레핀 소재
자동차소재 (PP, PP compound)
PE Pipe (portable water and gas supply)
LTHS(Long Term Hydrostatic Strength) ⇒ 50년 수명 보장
Encapsulation Layer of Solar Cell (EVA)
Ethylene-Vinylacetate copolymer
EVA Sheet
UHMWPE (Ultra High Molecular Weight PE)
• 인장강도, 내마모성, 내충격성 탁월
방탄복
Battery Separator Film (LIBS) – UHMWPE
Porous film for LIBS
Extrusion (압출성형)
Injection Molding (사출성형)
Blow Molding (중공성형)
Rotomolding (회전성형)
Compression Molding (압축성형)
Calendering (캘린더링)
Casting (캐스팅)
Vacuum Foaming (진공성형)
Foaming (발포성형)
Film
Extrusion
Injection Molding
PE, PP 수지의 가공방법
폴리올레핀 제조공정
올레핀 중합공정
Catalyst
Pre-polymerization
Polymerization
Separation/Drying
Extrusion
Monomers
PE/PP Pellet
+
Mild polymerization at low temp (10~30℃) for better polymer morphology
Removal of solvent & residual monomers
CH2=CH-R
Co-catalyst +
AlEt3
Additives
Monomers Solvent
중합공정의 종류
중합조건에 따른 분류
Solution process (high temp)
Slurry process
- Diluent slurry (iso-butane, n-hexane)
- Bulk slurry (liquid C3”)
Gas-phase process
반응기 형태에 따른 분류
Autoclave Reactor for LDPE
Tubular Reactor for LDPE (PFR)
CSTR (Continuous Stirred Tank Reactor)
Loop reactor
FBR (Fluidized Bed Reactor)
MZCR (Multi-Zone Circulating Reactor)
200~300℃, 1300~2000 bar
ICI (1938)
Autoclave LDPE Process (radical polymerization)
200~350℃
2000~3200 bar
BASF(1953) Lyondell Basell
Tubular LDPE Process (radical polymerization)
CSTR (Continuous Stirred Tank Reactor)
Mitsui’s CX HDPE Process (Hx slurry, 80℃)
Mitsui’s Hypol PP Process (C3” bulk, 70℃)
Hoechst HDPE Process (Hx slurry)
Solution PE Process (150~350℃)
Multi-reactors for broad MWD
#1 #2
Mw(1) Mw(2) ≠
Loop Reactor
• Phillips PE process (iso-butane slurry)
• LyondellBasell’s Spheripol PP Process (C3” bulk slurry)
FBR (Fluidized Bed Reactor, Gas-phase)
• Unipol PE, PP Process • BP LLDPE Process
MZCR (Multi-Zone Circulating Reactor, Gas-phase)
• Spherizone PP Process (LyondellBasell)
Residence Time Distribution
폴리올레핀 종류별 중합공정
올레핀 중합 촉매
1. Ziegler-Natta 촉매
2. Metallocene 촉매
Catalyst in olefin polymerization
Classification of Catalyst Types
Peroxides → LDPE, EVA 250~350℃, 2000~3000 atm
R O C OO C O R
O O
R C
O
OO C R
O
Ziegler-Natta catalysts → PE, PP
TiCl4/MgCl2, TiCl4/MgCl2/SiO2 : PE
TiCl4/ID/MgCl2 : PP
Phillips catalyst → PE (HDPE, MDPE)
Cr-type supported in SiO2
Single-site catalysts → PE, PP, POE
Metallocenes
Non-metallocene (Post-metallocenes)
(Peroxides)
Catalyst Technology Evolution Timeline
Phillips Catalyst
Catalytic sites for ethylene polymerization
Nobel Prize in Chemistry (1963)
Ziegler-Natta Catalyst
Prof. Karl Ziegler (1898~1973, Germany)
Prof. Giulio Natta (1903~1979, Italy)
Discovered TiCl4/AlEt2Cl catalyst for polyethylene at the Max-Planck Institute in Mülheim (1953)
Discovered isotactic polypropylene at the Polytechnical Institute of Milan (1954).
Historical development of Z-N catalyst
Mechanism for Ziegler-Natta Catalysis
Isotactic PP
Atactic PP
Syndiotactic PP
• High Tm (161~164℃) • High modulus • Most of commercial PP
• Low Tm (Tm 130~140℃) • Low modulus • Meta-stable crystalline structure • Not successful in commercialization
• Amorphous and sticky • Used for limited application (hot melt)
Molecular Structure of Polypropylenes
31-helical structure of iso-PP crystal
Generations of polypropylene catalysts (generations)
Commercial Z-N Catalysts for PP
Activator (cocatalyst) : Al(Et)3 ; Ti(4+) → Ti(3+)-Et
External electron donor: R2Si(OCH3)2 ; istacticity ↑
Ionic radius
Mg2+ 0.68 Å
Ti4+ 0.65 Å
Catalyst support : MgCl2
Active species : TiCl4
Internal electron donor : Phthalate, Diether, etc.
Main catalyst
Cocatalyst
Cl
Ti
Mg
π-orbitals of olefin monomer (ethylene)
The electrons from olefin’s π-bonding fit nicely into the empty orbital of titanium
The electrons from one of the filled orbitals can slip into the olefin’s π-antibonding orbital, making the titanium-olefin complex stronger (back donation)
Titanium-Olefin Complex
Propylene Insertion Mechanism
Propylene >5,000 units/Ti*/sec Polymer >1 개(Mw 20만)/Ti*/sec
Stereoregularity of Z-N Catalysts
1 1
2 2 3 3
Prochirality of adsorbed propylene
Corradini et al. Acc. Chem. Res. 2004
si-enantioface
ED
Ti
Mg
propylene
C
Mg
Cl Ti
polymer chain
ED
re-enantioface
Stereoselective propylene insertion
Adsorption of Internal Donors on MgCl2
Three types of adsorption modes on MgCl2 surface
Chelate Mode on (110)
Bridge Mode on (110) and (100)
Zip Mode on (110)
zip
(110)
bridge
bridge
chelate
MgCl2 support
Correa et al. Macromolecules 2007
Catalyst & Polymer Morphology
Replication of catalyst morphology
5min 20s 2hrs
Porous catalyst
Non-porous catalyst
Fragmentation of catalyst particle
6 sec(1.8g-PP/g-Cat) 1 min (10-14 g-PP/g-Cat) 30 min (450 g-PP/g-Cat)
Dark spots : catalyst fragments
Monomer diffusion effect
Idealized simulation to demonstrate the effect of
particle morphology on mass transfer resistance
R
r CBulk
C
C, CBulk : Monomer concentration
r : Distance from particle center
R : Radius of the particle
III
II
I III : Intrinsic activity of a very porous particle
(no diffusion limitation)
Rp(r) = k(t)*C(r, t)
올레핀 중합 촉매
1. Ziegler-Natta 촉매
2. Metallocene 촉매
Metallocene Complexes ?
Ferrocene “Sandwich structure” (G. Wilkinson & R. B. Woodward, 1952)
?
Ferrocene
6e-
6e-
d6e-
18e-
(stable)
2+
M = Ti, Zr, Hf
-
-
Metallocene catalysts for polyolefins
Professor Walter Kaminsky (University of Hamburg)
1952 Ferrocene (Fisher & Wilkinson) 1973 Addition of small amount of water increased activity (Meyer & Breslow) 1977 Discovered MAO (AlMe3+H2O) and high activity Cp2ZrMe2/MAO system (W. Kaminsky & Sinn) → 10,000 times increase of catalyst activity “Kaminsky Catalyst” 1982 C2-symmetry ansa-metallocene (Brintzinger) 1984 Isotactic PP from ansa-metallocenes (John A. Ewen)
Historical development of metallocene catalysts
PE catalyst technoloty Evolution Timeline
Examples of Metallocene Catalysts
C2-symmetry (ansa-metallocene)
Isotactic PP
For polyethylene
For polypropylene
Syndiotactic PP
Cs-symmetry
LLDPE, POE
rac-Et(Ind)2ZrCl2 (ansa-metallocene)
Stereoselective insertion of monomers
Cocatalysts for Metallocenes
MAO (methylalumoxane) Borane & Borate
Plausible structures of MAO
Polyethylene
Metallocene Ziegler-Natta
• Narrow MWD • Broad MWD
• Homogeneous
comonomer
distribution
• Heterogeneous comonomer distribution
• High dart impact strength & optical property
Metallocene Ziegler-Natta
• Narrow MWD • Broad MWD
• More insertion errors
• Less insertion errors
• Lower hexane- extractable
• Higher Tm and higher flex. modulus
Isotactic Polypropylene
Metallocene vs. Ziegler-Natta
한화토탈의 촉매기술
촉매개발 및 상업적용사례
Polyolefin R&D
R&D
Product & application
Catalyst Process
Morphology
Isotacticity
C2=, C4= response
Mol. wt Distribution
H2 response
Activity
Catalyst Design
Support
I/D, E/D
I/D, E/D I/D, E/D
Support, I/D
Support, I/D
물성
가공성 물성
공정운전성
생산성
공정운전성 (MI 조절)
제품범위 (random, ter, block)
I/D (Internal Donor) E/D (External Donor)
핵심요소기술
한화토탈의 촉매기술 개발
DMol3 program included in Material Studio
Cluster model to describe (110) and (100) surface of MgCl2 support
Spin-unrestricted electronic state to calculate Ti3+ electronic state
Computational Calculation (DFT)
Theoretical Approach for Catalyst Design
Prediction of catalytic activity and isotacticity from internal and external donors’ structure
Design of new internal donors
Development of new high performance catalysts
Prediction of catalyst activity
Background
Phthalate Donors
Chelate mode
Zip mode
ΔEad =-42.7kcal/mol
ΔEads = -43.3 kcal/mol
Prediction of isotacticity
각 공정별 특화된 고성능 촉매기술
HDPE LLDPE PP (Hypol) PP (Spherizone)
①일반 HDPE용 고활성 촉매
②미분체형 PE용 촉매 (morphology 우수)
③UHMWPE용 촉매
①고투명, 고장력 필름용 metallocene 촉매
②LDPE-like LLDPE용 Met 촉매
①고활성/고입체규칙성 촉매 (25㎛, 球形)
②Non-phthalate PP 촉매
①고활성/고입체규칙성 촉매 (70㎛, 球形)
Z-N 촉매
Z-N 촉매
담지형 Metallocene
고활성 Z-N
CMR-free Z-N
고성능 Z-N
촉매 문제에 의한 공정 트러블 사례 (Pilot Plant)
촉매 morphology 불량 (BD, fines), 과반응
고성능 PP 촉매 (excellent activity and morphology)
Polymer Catalyst particles
울산석유화학단지
여수석유화학단지
대산석유화학단지
한화토탈
한화종합화학
LG화학
롯데케미칼
현대오일뱅크
한화토탈
(Hanwha Total Petrochemical Co., Ltd) 매출(2015): 8.3조원
에틸렌 생산능력: 109만톤/년
주제품: 합성수지, 기초유분/화성제품, 석유제품
합성수지 142만톤/년
- LDPE/EVA 40만톤, HDPE/LLDPE 30만톤,
PP 72 만톤
R&D 분야
촉매(중합, 화성)
수지제품
복합수지
공정
화성/에너지
선행기술
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