s3_4_ÀÓÁ¾¼º_kstp_2012

Thermal Properties of Recycling for Phenol Resin using Supercritical Fluid.

초임계 유체를 이용한 재활용 폐 페놀수지의 열물성 연구

2012. 4. 6

조항규, 임종성*

서강대학교 화공생명공학과

Contents

Introduction

Objectives

Materials & Experiments

Results & Discussion

1

2

3

4

Conclusions 5

Supercritical Processing Lab

x1

0.2 0.4 0.6 0.8

Pre

ssur

e(M

Pa)

0

20

40

6030 oC40 oC50 oC60 oC70 oC80 oC90 oC100 oC

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

x1, y1 (DME mole fraction)

Pres

sure

(MPa

)

나노분말사출성형체(PIM)로부터 결합제 제거

초임계 유체를 이용한 고분자 나노입자 제조

3차원 나노구조 제어를 통한 광구조체 제조

이온성액체(Ionic Liquid)의 물성•용해도 측정 각종 혼합물의 열역학적 물성 및 상평형 측정

나노입자 제조

이온성 액체

상평형

초임계 추출

나노구조 제어

SCF Technology

고분자 재활용

초임계 유체를 이용한 열경화성 수지 재활용

약물전달체(DDS)용 나노 입자 제조

3차원 광구조체 Base

Lead-in wire

Ceramic Bulb

Outer Bulb Electrodes

Support

Frame wire connection Frame wire

Introduction

Phenol Composite

Supercritical fluid

Phenol

Carbon

- Graphite

- Carbon Black

- Activity Carbon

- CNT

- Fullerenes

- 자동차 : 내장재,브레이크라이닝, 필터

- 철강 : 주물, 내화벽돌

- 접착제 : 잉크, 페인트

- 전기/전자 : PCB, EMC, 에폭시 중간체

- 토목/건축 : 확장판, 절연재, 단열재

Supercritical fluid technology for recycling of plastic wastes

1. Sumitomo Bakelite Co. Ltd. (Japan) ;

- thermosetting : phenol, epoxy, polyimide, melamine resins.

2. 應用科學硏究所 (Japan); fiber reinforced unsaturated polyester FRP resin

3. Chubu Electric Power Co. Inc (Japan) ; XLPE from cable jackets

4. KOBE Steel and NTT (Japan); thermoplasticization of plastic wastes

5. Tohoku Electric Power, Mitsubishi Heavy Industries (Japan) ;

- thermoplasticization by supercritical water

6. Auburn University (USA); Depolymerization of crosslinked SBR

Supercritical Fluid

Liquid

- Density

- Solvent power

Gas

- High diffusion rate

- Low viscosity

- Low surface tension

Objectives

1. To understand the thermoplasticization mechanism of phenol

resin by using supercritical methanol.

2. To develop the optimum conditions for recycling of phenol

resin.


□ Phenol resin : Yoowon, YW-BA-PB □ Methanol : 100% □ LDPE(Low Density Polyethylene) : Hanwha chemical, 5315

■ Materials

■ Preprocessing

Phenol resin Cutting


Manufacturing process overview

Mixing Treating Pressing

+ +

+ +

+ +

Packing Cutting & Inspec


PG Cooling line (Out)

Cooling line (In)

Heater Temperature : 1000℃

Reactor (SUS316) Capacity : 500ml DP/DP : 690bar/500℃

Controller

Results and Discussion

Sample Type Size Sample

(g) Methanol

(g) Temp.

(℃) Pressure

(bar) Time (min) Note

Pellet 0.7~0.5㎜ 10 70 380 171 1

Size Powder 1~0.56㎜ 10 70 380 170 1

Powder 600~400㎛ 10 70 380 173 1

Powder 355~224㎛ 10 70 380 172 1

Pellet 0.7~0.5㎜ 10 70 380 172 1

Methanol Pellet 0.7~0.5㎜ 10 100 380 223 1

Pellet 0.7~0.5㎜ 10 130 380 272 1

Pellet 0.7~0.5㎜ 10 150 380 311 1

Pellet 0.7~0.5㎜ 10 70 230 89 1

Temperature

Pellet 0.7~0.5㎜ 10 70 280 98 1

Pellet 0.7~0.5㎜ 10 70 330 139 1

Pellet 0.7~0.5㎜ 10 70 400 186 1

Pellet 0.7~0.5㎜ 10 70 420 206 1

Pellet 0.7~0.5㎜ 10 70 380 172 10

Time Pellet 0.7~0.5㎜ 10 70 380 171 30

Pellet 0.7~0.5㎜ 10 70 380 172 60

Pellet 0.7~0.5㎜ 10 70 380 172 120

Pellet 0.7~0.5㎜ 10 100 380 177 1 Ethanol

Pellet 0.7~0.5㎜ 10 100 380 125 1 Acetone

Pellet 0.7~0.5㎜ 10 100 380 219 1 Water

Pellet 0.7~0.5㎜ 10 100 380 172 1 Methanol


Methanol 380℃ 172bar


Ethanol 380℃ 177bar

Acetone 380℃ 125bar

Water 380℃ 219bar

Liquid

Solid





Water 380℃ 219bar

Phenol resin

Methanol 239.45℃ 80.9bar

Acetone 234.950℃ 47bar

Water 374.5℃ 221.2bar

Ethanol 240.75℃ 61.4bar

Supercritical Point

Results and Discussion Methanol 380℃ 172bar



Water 380℃ 219bar

Methanol Acetone Water Ethanol

Raw Solvent 2.18 0.47 6.17 2.18

SCF 805 192.4 2.31 206.4

메탄올량 온도 압력 시간 전기전도도 (g) (℃) (bar) (min) (㎲/㎝) 70 280 98 1 365 70 330 139 1 673 70 380 172 1 923 70 400 186 1 1094 70 420 206 1 1218


380℃, 70G, 172bar 380℃, 100g, 223bar

380℃, 130g, 272bar 380℃, 150g, 311bar

Effect of Methanol/Pressures


280℃, 98bar 330℃, 139bar 380℃, 172bar

400℃, 186bar 420℃, 206bar

Effect of Temperature


X1.0K X6.0K

Recycle Carbon : 380℃, 223bar, Methanol(100g), 1min

30㎛ 5㎛

2~3㎛


Recycle Carbon : 380℃, 223bar, methanol(100g), 1min

Intermixer

Recycle Carbon Polyethylene : 50g

Hotpress

200℃, 100RPM, 10min 220℃, 10ton, 7min


Intermix: 200℃, 100RPM Polyethyelene : Recycle Carbon (0.1, 0.3, 0.5, 0.7, 1, 3, 5, 7, 10phr)

Polyethylene 0.1phr 0.3phr 0.5phr 0.7phr

1phr 3phr 5phr 7phr 10phr


Phenol resin LDPE + Recycle Carbon (50g) (5g)

Recycle Carbon

Raw LDPE


Intermix: 200℃, 100RPM Polyethyelene : Recycle Carbon (0.1, 0.3, 0.5, 0.7, 1, 3, 5, 7, 10phr)

Polyethylene 0.1phr 0.3phr 0.5phr 0.7phr

1phr 3phr 5phr 7phr 10phr

100 200 300 400 500 600

0

20

40

60

80

100

W

eigh

t (%

)

Temperature (oC)

0phr-RC 1phr-RC 3phr-RC 5phr-RC 7phr-RC 10phr-RC

Polyethylene (50g) : RC(Recycle Carbon)


40080

100

Wei

ght (

%)

Temperature (oC)

TGA (Thermogravimetric Analysis)


0 50 100 150-2

0

2

4

6

8

10

Polyethylene (50g) : RC(Recycle Carbon)

10phr_RC7phr_RC5phr_RC3phr_RC1phr_RC

He

at F

low

(W/g

)

Temperature (oC)

0phr_RC

DSC(Differential Scanning Calorimeter)

40 60 80 100

0

50

100Polyethylene (50g) : RC(Recycle Carbon)

Di

men

sion

Chan

ge (µ

m)

Temperature (oC)

0ph_RC 1phr_RC 3phr_RC 5phr_RC 7phr_RC 10phr_RC


TMA (Thermomechanical Analysis)


0

5

10

15

20

25

30

Tens

ile st

ress

(MPa

)

phr0 1 3 5 7 100

200

400

600

800

1000

1200

1400

Impa

ct E

nerg

y (J)

phr0 1 3 5 7 10

인장강도 충격강도

Conclusions

1. Phenol resin은 초임계 메탄올 반응을 이용하여 카본입자로 재활용 할 있음을 확인하였다.

2. 초임계 메탄올에서의 반응은 반응압력, 반응매체의 양보다 반응온도에 의한 영향이 더 컸으며

반응온도가 증가함에 따라 카본입자 생성이 촉진된다.

3. 재활용 카본입자를 첨가하였을 경우, internal mixer내의 토크 값의 증가에 의해 물성이 향상.

4. 카본입자를 사용하여 LDPE와 blend 하였을때 순수 LDPE보다 열안정성이 향상.

페놀수지

Resol & Novolac Comparison

Novolac Resol

Appearance Solid Liquid

Reaction

F/P (mole) < 1 > 1

Catalyst Acid Alkali

pH 1 ~ 4 >5

Structure Structure Methylene Bridge Methylol End Group

M.W 700 ~ 2500 500 ~ 1500

Curing Needs hardener Can be cured by Heat

s3_4_ÀÓÁ¾¼º_kstp_2012

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