超臨界流体と共に歩んだ名古屋と熊本での38年
38 years in Nagoya and Kumamoto
along with supercritical fluids

名古屋大学
大学院工学研究科 物質プロセス工学専攻

後藤元信
⼯学研究科1号館2階121講義室
2022年3⽉10⽇14:00-15:00

1

Biodata (Motonobu Goto)
1984 Dr. Eng., Nagoya University
1984 Assistant Professor, Nagoya University
1988 Associate Professor, Kumamoto University
1988 California University, Davis（15 months)
2001 Professor, Kumamoto University
2012 Professor, Nagoya University
2013 Super Critical Technology Centre Co. Ltd.
Vice-President of The Society of Chemical Engineers, Japan (2016-7)
Vice-President of The International Society for Advancement of Supercritical Fluids
2
Associate Editor of The Journal of Supercritical Fluids
President of Research Association For Feedstock Recycling of Plastics Japan (2016-7)

Event in my researcher life on SCF
1988 Nagoya University名大→ Kumamoto University熊大1988 California University, Davis（15 months)

Prof. T. Hirose

1993 NATO Advanced Study Institute on Supercritical Fluids（Turkey）
1996 JSPS Research for the Future Program未来開拓学術研究推進事業【1996-2000】荒井康彦
1997 MESC Scientific Research on Priority Areas重点領域研究【1997-2000】超臨界
2003 21 century COE Program (Kumamoto Univ)【2003-2007】
2006 8th International Symposium on Supercritical Fluids (Kyoto) Organizer
2008 Global COE Program (Kumamoto Univ) 【2008-2012】2009 MEXT Scientific Research on Innovative Areas新学術領域研究【2009-2013】プラズマ2012 Kumamoto University 熊大→ Nagoya University名大2013 Workshop on Supercritical fluids and Energy in Brazil
2013 Super Critical Technology Centre Co. Ltd. 超臨界技術センター㈱ 設立 名大発ベンチャー2017 Supergreen (10th International Conference on Supercritical Fluids) Nagoya
3

University of California, Davis

1988.10-1989.12

Benjamin J. McCoy J. M. Smith

Supercritical fluid
Mathematical Modeling

Kumamoto U.

Istanbul, Turkey

UCDavis 2001

4

Event in my researcher life on SCF
1988 Nagoya University名大→ Kumamoto University熊大1988 California University, Davis（15 months)

Prof. T. Hirose

1993 NATO Advanced Study Institute on Supercritical Fluids（Turkey）
1996 JSPS Research for the Future Program未来開拓学術研究推進事業【1996-2000】荒井康彦
1997 MESC Scientific Research on Priority Areas重点領域研究【1997-2000】超臨界
2003 21 century COE Program (Kumamoto Univ)【2003-2007】
2006 8th International Symposium on Supercritical Fluids (Kyoto) Organizer
2008 Global COE Program (Kumamoto Univ) 【2008-2012】2009 MEXT Scientific Research on Innovative Areas新学術領域研究【2009-2013】プラズマ2012 Kumamoto University 熊大→ Nagoya University名大2013 Workshop on Supercritical fluids and Energy in Brazil
2013 Super Critical Technology Centre Co. Ltd. 超臨界技術センター㈱ 設立 名大発ベンチャー2017 Supergreen (10th International Conference on Supercritical Fluids) Nagoya
5NATO Advanced Study Institute on Supercritical Fluids
Kemer, Antalya, Turkey, 1993.7.18-31

Erdogan Kiran

Feral Temelli

Stephane Sarrade"Supercritical Fluids Fundamental and Applications”,
Erdogan Kiran, Pablo G. Debenedetti, Cor J. Peters,
NATO Science Series(NSSE) volume366
Springer, 2000

6

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
7

Supercritical Fluid

Solid

SupercriticalState

LiquidMeltingFreezing

Critical point
Condensation
Vaporization
Triple point
Deposition
Sublimation

Temperature

Gas

CO2
Methanol
Water

Tc [K]
304.15512.6
647.3

Pc [MPa]
7.38
8.09
22.12

Supercritical Fluid
Gas like property- High diffusivity
Property of SFCs
-Low viscosity- Low surface tention
SUPERCRITICAL- High density- High solvation power

LIQUID

SOLID

Density of CO2

GAS

Liquid like property

9Extraction
Solubility of 2,3-dimethylnaphthalene in carbon dioxide

Density of solvent
Vapor pressure

Solubility

Supercritical Fluid

Property of water
Dielectric constant

Ion producthexisane

1.8(20℃)

benzene2.28(20℃)

acetone20.70(25℃)

ethanol

24.55(25℃)

methanol

32.63(25℃)

High dissolution powercomparable to organic solvent

Hydrolysis proceed w/o catalyst
due to the strong acidic and basic
property11

Supercritical Fluid
Typical Application of SCFs
Solvent polarity

low

high

Supercritical
CO2

Supercritical
CH3OH

Supercritical
H２ O

31℃, 72 bar

240℃, 81 bar

374℃, 221 bar

Higherreactivity

Lower
reactivity
Extraction
Separation
Cleaning
DyeingFoaming
Nanomaterial preparation

Depolymerization
Alkylation
Alcoholysis

Environmental friendly process

SCWO
POPs destruction
Nanomaterial synthesis
Extraction (Subcritical)

12Supercritical Fluid
Hybridprocess
Modeling

Countercurrent
process

Adsorption
process
Isomerization

Separation

Extraction

Recycling

Microwave

Micronization
Ultrasonic

ReactionMicrodeviceMaterial
processing

PlasmaLaser

Electrostatic
13

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
14

Start-up SCF laboratory at Kumamoto University (1990)
Prof. T. Hirose

1998
Prof. T. Kobayashi

Extraction apparatus from Prof. Kobayashi

Supercritical CO2 extraction apparatus

HPLC

15

Extraction – Modeling Extraction modelingCssupercritical fluid

solid
pore

film

Cp

Extractor

flow

solid matrix

C
Dp

kf

Cs
Ds

Cp
kd

ka
Cs

16

Extraction – Modeling Extraction modelsnDiffusion modelnnShrinking-core modelnn

M. Goto, B. C. Roy, A. Kodama, and T. Hirose, "Modeling Supercritical Fluid Extraction Process
Involving Solute-Solid Interaction", J. Chem. Eng. Japan, 31, 2, 171-177, 1998

Solute-solute interaction modelnn

B. C. Roy, M. Goto, T. Hirose, O. Navaro and O. Hortacsu, “Extraction Rates of Oil from Tomato
Seeds with Supercritical Carbon Dioxide”, J. Chem. Eng. Japan, 27, 6, 769-773, 1994

Solute-solid interaction modelnn

M. Goto, B. C. Roy, and T. Hirose, “Shrinking-Core Leaching Model for Supercritical Fluid Extraction”, J.
Supercritical Fluids, 9, 2, 128-133, 1996

Heterogeneous modelnn

M. Goto, M. Sato and T. Hirose, “Extraction of Peppermint Oil by Supercritical Carbon Dioxide”,
J. Chem. Eng. Japan, 26, 4, 401-407, 1993

N. T. Dunford, M. Goto, and F. Temelli, “Modeling of Oil Extraction with Supercritical CO2 from
Atlantic Mackerel (scomber scombrus) at Different Moisture Contents”, J. Supercritical Fluids,
13, 13, 303-309, 1998

Continuous-mixture modeln

M. Goto, T. Hirose, and B. J. McCoy, “Continuous-Mixture Model of Extraction Processes,17J.
Supercritical Fluids, 7, 61-66, 1994

Extraction – Modeling Shrinking-core leaching modelDe ¶ æ 2 ¶Ci ör
÷ =0
2 ¶r ç
èø¶rr

C s ,av C s ,0 = (rc R )3

Ci (r = rc ) = C r

rc (t = 0) = R

18

Separation – Modeling Continuous-Mixture Model of Extraction Processes

UCD/Ben. J. McCoy

19

M. Goto, T. Hirose, B. J. McCoy, J. Supercritical Fluids, 7, 61, 1994

Extraction – Modeling -20

By Prof. Richard SmithSeparation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
21

Separation - Countercurrent Extract
Enriching
Section

Feed

Countercurrent extraction
Deterpenation of citrus peel oil

Stripping
SectionRaffinate

Composition of extracts [wt%]

SCF

70
60
50
40
30
20
10
0
0

50

100

150

200

Time [min]

250

300

22

Separation - Countercurrent Separationof problem
Fatty Acid Methyl
Conventional method
and its
Esters and Tocopherols
Tocopherols (Vitamin E)
with Supercritical CO2
Dr. Tao Fang
Supercritical CO2
Molecular or
vacuum distillation
Methyl esterified DOD(ME-DOD)Supercritical MeOH
Sterols

Methyl esterification ( H2SO4)

Soybean deodorizer distillate(abbreviated as “DOD” )Soybean oil
industry

China

Korea
23

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
24Separation - Adsorption Supercritical Pressure Swing Adsorption Process
Feed dissol ved in CO 2
half cycle timeTimecolumn 1

Desorpti on st ep

Adsorption step

Pressurization step

8.8

Rinse step

Pressure [MPa]19.4

Blowdown step

oxygenat edcompounds

terpenes

column 2Timeterpenes

half cycle time
pure CO 2

Dr. Masaki Sato25

Separation - Adsorption Supercritical Pressure Swing Adsorption Processcollaboration

100

Concentration factor

[-]

10

1

0.1

0.01

Adsorption
Rinse
Desorption
Blowdown

0.001
0

0.5

1

1.5

2

2.5

3

QD/QA [-]

Lemon oilOrange oil
Bergamot oil
Squalene/tocopherol
Feed

Terpenes

Oxygenatedcompounds

Wax
Pigment

Bergamot Oil

26

Separation - Hybrid processHybrid extraction process （sc-CO2+Liquid Water）

Hydrophobic

Hydrophilic

Organic solvent
extraction
Simultaneous separation is proposed
Hydrophobic
Extract

Water
extraction,
Steam
distillation

H2 O

NaturalProducts
SCCO2

Hydrophilic
Extract

27

Separation - Hybrid processHybrid SFE with CO2 and waterHot-water Extraction(subcritical water)

scCO2 Extraction
Target Material

Polarity ・Molecular weight
Essential

Oil

Terpenes

Flavonoid

lipidsProtein
Saccharides

GlycosideHybrid SFE with CO2 and water
Green solvent process

Halal production process
28
https://halalfocus.net/eu-introducing-the-european-halal-initiative/ 2022.5.27

Separation - Hybrid processHybrid extraction process （sc-CO2+Liquid Water）
scCO2＋target material

Hydrophobic component

H2 O

Hydrophilic component

Supercritical CO2
with dissolved
water

H2O
wet

Target material

dry

scCO2
Raw material

Water with
dissolved CO2(lower pH)

H2O＋polar
substance

Swollenmaterial

scCO2［continuous;H2O, dispersion;scCO2］
29

Separation - Hybrid processHybrid extraction process
Chlorogenic acid and caffeine from green coffee bean
O
HO

H3C

OH

HO
HO

O

HO

O

O

Chlorogenic acid

Chlorogenic
acid

40
30

caffeinec

20
10

N

CO2 phase

4.5

Caf. 0mm

4
Recovery of caffeine [%]Recovery of components [%]50

Chl. 0mm
Chl. 200mm
Chl. 300mm
Chl. 400mm

N

Caffeine

Water phase
Caf. 0mm
Caf. 200mm
Caf. 300mm
Caf. 400mm

N

N

CH3

O

60

CH3

caffeine

Caf. 200mm

3.5

Caf. 300mm

3

Caf. 400mm

2.5
2
1.5
1
0.5

0
0

100

200
Time [min]

300

400

0
0

50

100

150

200
250
Time [min]

300

350

400
30

Separation - Hybrid processHybrid extraction process

Flavonoids extraction from citrus peel
Low polarity

High polarity
OH

MeO

HO

MeO
O

OR

O

OMe
O

OR

OMe
OMe

O

OH

Naringin(R: neohesperidose)

0.025

30

30 MPa

0.015
0.01
0.005
2
3
4
Extraction time [hour]

80 oC
100 oC

20
15
10
5
0

0
1

20
15
10

30

30 MPa25

80 oC
100 oC

0.02

0

80 oC
100 oC0

Nobiretine [µg]Hesperidin [g]

0.03

25

Polymethoxyflavon5
oid in CO2 stream
0

Hesperidin in water
stream0.035

30

Nobiretine 30 MPa

Tangeretin

Nobiretine [µg]Hesperidin(R: rutinose)

OH

OMe

Tangeretine [µg]

O

O

5

30

0

1

2
3
4
Extraction time [hour]

5

1

2
3
4
Extraction time [hour]

5

2
3
4
Extraction time [hour]

530 MPa25

80 oC
100 oC

20
15
10
5
0

0

1

31

Separation - Hybrid processExtraction of pectin with subcritical water and CO2
80
80.00

Yield [%]

75

76.86
73.71
70.57
67.43

65

The hydrolysis of pectin molecule wasenhanced by increasing in the concentrationof carbonic acid in subcritical water.

78 %

70

64.29

60

61.14

5
10

58.00

a]
[MP
sure
Pres

15
20

150

Mw [kDa] (pullulane)

140

25
30

130
120

o

]
ture [ C
Tempera

92 %

100

140

60
50

none
10MPa
20MPa
30MPa

40
30
20

100

80

0

60
10

30

50

70

35000

90 110 130 150 170 190

S/F ratio (g H2O/ g sample)

Extraction yield of pectin increased withpressure (dissolved CO2)

104

25000
15000
5000
-5000

Temperature

10

RI response

Yield [%]

70

Temperature [oC]

120

105

none
10 MPa20 MPa30 MPa

45000

90
80

106

55000

6

7

8

9

10

11

Retention time [min]Molecular weight of pectin was controlled bypressure (dissolved CO2)
32

Separation - Hybrid processDestruction of Dioxins by combined process of
extraction, adsorption, and SCWO

extraction
concentration

Cl

O

Cl

Cl

O

Cl

detoxified
solid

Adsorbent

Pretreatment

destruction
SCWO

Effluentgas

Adsorber
ReactordryingSc-CO2
adsorption

Oxydant
Water

Extractor

Solidcontaining
dioxins

Fly ashDr. S. Kawajiri

Separator
Circulationpump
residue

water

NEDO Project [2000-2004]
Nagasaki Ryoden Technica
Kumamoto University
Shizuoka University

33

Separation - Hybrid processDestruction of Dioxins by combined process of
extraction, adsorption, and SCWO
DioxinsFirst
enrichment

Pretreatment

Dioxins
Secondenrichment

Extraction

Heavy
metals

SC-CO2Extraction residue

Dioxins
Third
enrichmentConcentration
adsorption

Supercritical water

Destruction
SCWO

Effluen
t gas

water

34

Separation - Hybrid processDestruction of Dioxins by combined process of
extraction, adsorption, and SCWO
Nagasaki Ryoden Technika / Shizuoka Univ.

Bench Plant

Extractor: 30 litter
Adsorber: 300 ml
SCWO reactor: 2 litter

Extraction/Adsorption

SCWO

35

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic36

Micronization
Particle Design with Supercritical Fluids Technology

Prof. Youn-Woo Lee (SNU)

RESS (Rapid Expansion of Supercritical Solutions)
GAS (Gas Anti-Solvent)SAS (Supercritical fluid Anti-Solvent)
ASES (Aerosol Solvent Extraction System)
SEDS (Solution Enhanced Dispersion by Supercritical Fluids)
PGSS (Particles from Gas Saturated Solutions)37

Micronization
SAS: Supercritical Anti-Solvent Crystallization
Solvent + CO2

GAS(Gas Ant-Solvent)

Solution

CO2

CO2

CO2
CO2

Solution

CO2
CO2

ASES
(Aerosol Solvent
Extraction System)

Solvent
38

Micronization

Carotenoids

b-carotene (C40H56)- Carotenoids are fat-soluble
plant pigment which have highly
vivid color.
- Their function for the human
body, such as antioxidant
activity, generates a great value
as high quality dietary
supplement and natural
colorants in food or medicine
industries.

Activity
・Anti-oxidant
・Anti-cancer
・dermatitis
prevention

MW: 536.87
CH3
CH3

CH3

CH3

H3C

CH3
CH3

CH3

CH3

CH3

chemical structure of b-carotene

Lycopene (C40H56)
Activity
・Anti-oxidant
・Anti-cancer
・Maintain bonedensity

MW : 536.87
CH3

CH3

CH3
CH3

H3C

CH3
CH3
CH3

CH3

CH3

chemical structure of Lycopene

Dissolve in organic solvent and oil
39

Micronization

SEDS process
Dr. Hazuki Nerome

SC-CO2lycopene/b-CyD

solutionCO2

solvent＋
soluteSoluteparticleCO2＋
solvent40

Micronization

Design of precipitator cell

Swirl Micro Mixer

Vessel type

Tube type

Micromixer type41

Curcumin/PVP particle

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
42

Isomerization
Z-isomerization in Supercritical Fluid Processing of Carotenoids

β-carotene
Dr. Masaki Honda

Improvement of functionalities→ absorbability and antioxidant capacity

Lycopene
LuteinChange of physical properties→ melting point, crystallinity and solubility

Astaxanthin
11 conjugated double bonds

5cis
9cis
13cis

all-trans-lycopene
・ plants

cis-isomers of lycopene
43
・ living animals・ processed foods

Isomerization
Solubility of lycopene

Effect of cis-isomers content【Solubility in methanol】
all-trans

0.1

40% cis20% cis179.3
25.8
Solubility (mg/L)

all-trans

Cr y
sta
l
40% cis【Solubility in various solvent】

70% cis635.1

20% cis

3 μm

→

3 μm

3 μm

70% cis

Am
orp

h ou

Solubility of lycopene in some organic
solvents greatly increases with highratio of cis-isomers

s
3 μm

44

Isomerization
Supercritical CO2 extraction from tomato■ Change in lycopene recovery

Llycopene recovery (%)

40

50 MPa, 50 ℃

30

75% cis tomato

20

30% cis tomato
1010% cis tomato

0
0

2

4
Time (h)6845Isomerization
Micronization of lycopene by SAS process
ー Solution enhanced dispersion by supercritical fluid (SEDS) ー

all-trans

63.5% cis3.6 µm

97.8% cis75 nm0.80 µm

5 µm

5 µm

5 µm
1 µm

46

Isomerization

47

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
48

Ultrasonic - Liposome Ultrasonic-assisted preparation of liposome using supercritical CO2
Liposome
Component

Phospholipids

Shape

Spherical
Lipid bilayer
Aqueous compartment

StructurellSpherical vesicles composed of one ormore phospholipid bilayers surrounding
discrete aqueous compartments.
Used as drug carriers in thepharmaceutical, cosmetic and foodindustry.

Application• Biomembrane• Drug carrier (DDS)

Small unilamellar vesicle
SUV (<100 nm)
Large unilamellar vesicle
LUV (100-1000 nm)
Multilamellar vesicle
MLV49

http://www.integratedhealth.com/supplements/liposomes.html. [Accessed: 1-Mar-2018].

Ultrasonic - Liposome Ultrasonic assisted supercritical fluid method
Supercritical CO2 method
Water containing
inclusion substance
W1 phase
SC-CO2 phase containing
inclusion substance
SC-CO2 phase

Only pressure reduction
CO2 removal

Ultrasonicationst

1 Emulsification

Ultrasonication
2nd Emulsification

W1/Oemulsion

W1/O/W2emulsion

High pressure

Small unilamellar vesicle
SUV (<100 nm)
Large unilamellar vesicle
LUV (100-1000 nm)
Multilamellar vesicle
MLV

Liposome

No residue oforganic solventUltrasonic - Liposome -Liposome

MixturePhosphatidylcholine (PC)Sphingomyelin (SM)

Dynamic Light Scattering (DLS)

Nanosight

25

Zeta Potential-17.6 (mV)

20
15
10
5
0
0

100

200

300

400

500
51

Ultrasonic - Liposome Effect of cis-isomer ratio on b-carotene content

b-carotene in liposome [mg]13Z

Cis form
Trans form
50℃, 10MPa（trans）
Isomer rate [%]

2.4%

37%

87%

52

Ultrasonic - Liposome -Cosmetics

Application of liposome
Liposome

Baby formula(milk)

Medicine

53

Ultrasonic - Liposome Bench plant installed in cosmetic company
Sphingomyelin

54

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
55

Reaction - Depolymerization Depolymerization of plastics using supercritical fluids
C O CH2CH2 O
n
O

C
O

Condensation
polymerization polymers
Ester bondEther bondAcid-amide bond

H2O

HO C
C OH
O
O
Terephthalic acidhydrolysis
CH3OH

H3C O Cmethanolysis
O

C O
O

+

OH CH2 CH2 OH
Ethylene glycol

CH3+

OH CH2 CH2 OH

Dimethyl terephthalate

SC-waterSC-alcoholOO(CH2)5

Solvolysis
Hydrolysis
Alcoholysis

PET

C

Nylon 6NH n

Chydrolysis
cyclodehydration(CH2)5NH

e-caprolactam

Chemical recycling of waste plastics

56

Reaction - Depolymerization Depolymerization of PET using supercritical methanol(COC O CH2CH2 O ) +
n
O

PET

2n CH3OH⇒

n CH3 O COMethanolC O CH3 + n HOCH2 CH2OH
O

DMT

EG

Population balance model (Distribution kinetics)
Polymer Melt Phasesc MeOHMeOH (L)Phase

MeOH (SC)Polymer (L)+ MeOH

RandomScissionkr_(L)
Oligomer (L)+ MeOHSpecific Scission ki_(L)MHET (L)kt_MHET+ MeOH

RandomScissionkr_(L)MHET (SC)+ MeOH

Secondary
Reaction

Specific
Scissionk’i_(sc)ki_(L)Monomer (SC)
(DMT, EG)ＭＨＥＴ (L)+ MeOH

kt_MHETＭＨＥＴ (SC)+ MeOH

Secondary
Reactionk’i_(sc)

57
Monomer (SC)
(DMT, EG)

Reaction - Depolymerization Depolymerization of plastics using supercritical fluids
Batch test Laboratory test
2000-2001
1998-1999

Bench test
2001-2002

Pilot test
2003-2005( A part of construction cost was
supported from Ministry of Economy,
Trade and Industry, Japan . )Road to commercialization
Dr. Minoru GentaReaction - Depolymerization Fiber reinforced plastics (FRP)
Depolymerization in
subcritical alcohol torecover fibers

Dr. K. Shibata

Benzyl alcohol/K3PO4
Polyester chain
O

O
O

O

O

O O
O

O

O
O

O O
O

O

O

O
O

O O
O

O

O

O

scission
Polystyrene
chain(Dissolve insolvent)

Ester
bond
O
O
O O

O

O

O
O

O
O O

O

O

O

O
O

O
O O

O

O

O
O
O

200L bench plant(Hitachi Chem.)）Ambient pressure -> High pressureReaction - Depolymerization FRP (fiber reinforced plastics)
Depolymerization in subcritical water for upgrade recycling
Dr. T. Nakagawa

Panasonic Inc.

0.4ｔ per operation
0.8ｔ per day(200 tons annually)Reaction - Depolymerization 総説論文

Reaction - Depolymerization -62

By Prof. Richard SmithEvent in my researcher life on SCF
1988 Nagoya University名大→ Kumamoto University熊大1988 California University, Davis（15 months)

Prof. T. Hirose

1993 NATO Advanced Study Institute on Supercritical Fluids（Turkey）
1996 JSPS Research for the Future Program未来開拓学術研究推進事業【1996-2000】荒井康彦
1997 MESC Scientific Research on Priority Areas重点領域研究【1997-2000】超臨界
2003 21 century COE Program (Kumamoto Univ)【2003-2007】
2006 8th International Symposium on Supercritical Fluids (Kyoto) Organizer
2008 Global COE Program (Kumamoto Univ) 【2008-2012】2009 MEXT Scientific Research on Innovative Areas新学術領域研究【2009-2013】プラズマ2012 Kumamoto University 熊大→ Nagoya University名大2013 Workshop on Supercritical fluids and Energy in Brazil
2013 Super Critical Technology Centre Co. Ltd. 超臨界技術センター㈱ 設立 名大発ベンチャー2017 Supergreen (10th International Conference on Supercritical Fluids) Nagoya
63

Separation

Reaction

Material

Supercritical fluid
Extraction and ModelingMicronization
Countercurrent
Hybrid process
Isomerization
Recycling
Ultrasonication
Micro device
Plasma and Electrostatic
64Plasma"Ionized" refers to the presence of
one or more free electrons, which are
not bound to an atom or molecule.

PlasmaKinetic Energy of Particles

PlasmaPlasma is an ionized
gas.

Gas
LiquidSolid
Temperature

Illuminant, Reactivity, Electrically conductive
Fast particle, High temperature

65Plasma

Semiconductor
https://sterilisatievereniging.nl/wp-content/uploads/2015/08/2013-03-presentatie-Jan-van-Dijk.pdf 2022.5.27

https://scorec.rpi.edu/research_plasmaetchmodeling.php 2022.5.27

Nuclear Fusion

PlasmaMedicalhttps://onlinelibrary.wiley.com/doi/abs/10.1002/ppap.201670036 2022.5.27

Agriculture

著作権の都合により画像を削除しました。
プラズマ水と植物の生育の関係を
示した図

66

Plasma

Discharge plasma in supercritical fluid
Supercritical CO2

T = 313K
P = 8.0MPa

Sub-critical
H2O

T = 563K
P = 10.0MPa

Collaboration with Prof. H. Akiyama group at Kumamoto University
since 2003 as 21st COE & GCOE.

Pulse power + Supercritical fluid

67

Plasma
Characterization of Breakdown Voltage Profile andSolvent Density
Vgave
Œð“_
measured SCF phasecalculated

40
Breakdown Voltage, VB (kV)35

Pressure, P (MPa)

25
15

20

10

15
gas phase

10

5

298K

supercritical phase

293K
283K

10
8

Pc

6 gas

304K
305K

12

C1

C2 B2 A4

333K 323K

14
C2

30

critical isotherm

313K

C1
B1

A3
A2

A1

liquid (P > Pc)
liquid (P < Pc)

8
9
4Y = M0 + M1*x criticalpointM8*x + M9*x
+ ...
(304.1K, 7.38MPa)

5
0

0

C

0

200

0 10 20 30 40 50 60 70

400
600
-3
Density, r (kg m )800

M027.763saturated 0.0054611
liquid line
M1
CBA
0
0
200 M2400
600
8005.5985e-06
1000-3Density,R r (kg m )0.819032

saturated gas line

In supercritical phase, the increasing rate of the breakdown voltage to density
becomes small far from liquid phase. In comparison with density curve of CO2, it isobserved that the increasing rate of breakdown voltages become smaller as the68phase approaches to saturated line.

Plasma
Discharge plasma at gas/liquid interface
Supercritical
argon

metal

Ionic
wind

UV
electronmetal ionshock Ar ion
wave
Ar radical

12

600

Current

8400

Current [A]Output Voltage [kV]Voltage

4

200

0

0

-4

-200

-8

-400

0

500

1000
time [nsec.]

1500

2000

Chemicalr
eaction Particle
Electrochemical formation
reaction
69

PlasmaPressure dependence of carbon nanoparticle generation
Starting material

XPS

glycineArgon Pressure
0.1 MPa 1.0 MPa 1.5 MPa 2.0 MPa 3.0 MPa 4.0 MPa

Carbon particle surface is modified
with carboxyl group（ｰCOOH）

Carbon particles are generated by discharge over 1.5 MPa

O
HO
C−

HOOC−

O
CO
−

H

4.0 MPa (6 month)

TEM images (4.0 MPa)

Raman

C
C −COOH
N
OO
−C
H

C−
O
HO

70

PlasmaTitania / carbon composite particle

HRTEM像(3.0 MPa)①②

Emission Spectrum

④

③

⑤

Photocatalytic Activity

Decomposition of methylene blue

0.1 MPa

1.0 MPa

1.5 MPa 2.0 MPa 3.0 MPa

STEM-EDS mapping
3.0 MPa
Ti
O

C

71

Plasma
Plasma at G/L Slug Flow in Capillary Tubetaken byhigh speed camera
supplyingvoltageAr

Flow rate controller

8 cm
Liquid pump

AC pulse
power supply

groundingFrequency 10 kHz

130
10 pulse/ frame
real time ×

350 pulse/ frame

NaCl aq

Voltage±9~12 kV

72

PlasmaInternal liquid circulation
2I-

Decomposition of naphthol blue black

I2 + 2e-212

Ag nanoparticle

Emission spectroscopy

TEM

50n
m

SＴＥＭ / EDX

50nm

Ag

O

73

PlasmaH.
V.

AC pulse unit

GND

Ar

Glass
tube

Flow reactor using
circular glass tube
with plasma

Slug flow plasma in glass column

Plasma -Pulsed laser ablation-

Radicals, ions,clusters,
electrons, light

Laser
Plume

vaporization
melt

Target material

vacuumgas

deposition
nano structured
material

etching
cavityliquidSCCO2

Plasma -Pulsed laser ablationLaser ablation in supercritical CO2
MirrorPulsed Nd:YAG Laser
10 Hz
532 nmValve
MirrorSafety valve
P

Aperture
TargetCO2 cylinder

Pump

Valve Filter

Glass slideHigh pressure cellwith sapphire window (SUS 316)
Pmax: 30 MPa
Tmax: 100 oC
Vmax: 0.11 L

Experimental Apparatus

Chiller

BPR

Flow meter76

Plasma -Pulsed laser ablationEffect of pressure

5 MPa

7 MPa

250
T = 40℃
T = 60℃

200

In air at ambientpressure

]
m150
[
h
t
p
e100
D

50

0
0

5

10
15
Pressure [MPa]2025Depth of irradiated gold plateincreased as increasing temperature.

Integrated optical emission intensity (arb. unit)

Optical Emission Intensity
3.0

5 MPa
7 MPa
8 MPa
10 MPa15 MPa

40℃

2.5
2.0
1.5
1.0
0.5
0.0
0

10

20

30

40

Delay time (ns)77

50

Plasma -Pulsed laser ablationSEM
In liquid CO2

Ni

Ag

Density

500 nm

500 nmTEM

metal

500 nmCore-shell structure

carbonElectrospinning
Fiber Fabrication by Electrospinning under Pressurized CO2

79

Electrospinning
Solid fiber

3.0 MPa, 37 oC

Low

Hollow fiber

5.0 MPa, 44 oC

Solubility of CO2 in solvent

Average: 6 µm

Balloon-likestructure

8.0 MPa, 45 oC

High

80

International Activity
Asian Society of Supercritical Fluids

M. Goto, T. Adschiri, B. X. Han, Y. W. Lee, Yan-Ping Chen
Ki-Pung Yoo, Ryuichi Fukuzato

Organizing Conference “Supergreen” in Asia

81

International Conference Organization
ISSF2006

Organizing Chairs:
Motonobu Goto
Tadafumi Adschiri
Buxing Han
Youn-Woo Lee
82

Supergreen 2017
M. GotoS. Takami

83

Workshop on Supercritical Fluids and Energy, Brazil,
2013.12.8-11
the current status and future directions of thesupercritical fluid science and technology

84International Activity
University of Valladolid, Spain
Prof. Maria Jose Cocero
PhD student: Oscar Benito and Teresa Moreno

Lecture in Spain by M. Goto
Lecture in Japan by M. Cocero
Visiting Prof.:
Dr. Juan García Serna

Visiting Prof.:
Dr. Angel Martin & María Dolores
Bermejo Roda85

University of Alberta, Canada
Prof. Feral Temelli
JSPS

Edmonton, Canada

Kumamoto Univ. & Kyushu Univ.
86

Institut Teknologi Sepuluh Nopember (Indonesia)
Dr. Siti Machmudah
Siti Machmudah

Exchange Agreement ITS & Nagoya U

Collaboration Lab at ITS

Profs of Chem. Eng.

Visit UBITS students to Nagoya U. by Sakura Science ProgramEge University (Turkey)
Prof. Oner Hortacsu, Bogazici Univ.

Exchange Agreement
Ege U & Kumamoto U

Ummihan Topal

Prof. Asli Yuksel
Izmir Inst. Tech.

Satellite (Liaison)
Laboratory on SCF

Prof. Ruhan Askin Uzel
Caner Uzelakcil
Yasar Univ.

Bulent Ozturk

Chulalongkorn University, Thailand
Prof. Artiwan Shotipruk
Prof. A. Shotipruk

Chulalongkorn U

With Chula students

PhD Congress

Former students of Chulalongkorn U

Nagoya and Chula students
Nagoya U office in Chulalongkorn U

89

International Society for
Advancement ofSupercritical Fluids

The Journal ofSupercritical Fluids

Vice-President
Associate Editor

Editor-in-Chief
Erdogan Kiran

90

Regional innovation creation research
地域イノベーション創出研究開発事業（九州経済産業局）

Development of functional food materials from
citrus fruit using green solvent technology
オレンジブロッサム

Coordinator: R. Fukuzato
Concentrated Terpeneless oil
柚子

Green orange

scCO2
scH2O

!
"
#

日
向
夏

橙

高品位柑橘果皮精油

Flavonoids

Green solvent platform

Yuzu

91
Pectin (functional food material)

Workshop on Supercritical Fluids
R. Fukuzato
M. Goto22 workshops since 2005
Lecture and Oversea plant survey
China
Korea
Taiwan92

Super Critical Technology Centre
Established in September 2013
KuwanaGoto & Fukuzato
Venture plan @Kumamoto University
Venture company foundation @Nagoya University + KEC
Focusing on extraction with scCO2
Approved as Nagoya Univ. Venture
Consulting
Contract R&D and production93Super Critical Technology Centre
Decaffeination of green coffee beans(30 L) pilot plant

decaffeinated coffeeCommercial plant (2019)

Decaf Green Tea

94

Acknowledgement• 共同研究者• 佐々木満、キタインアルマンド、児玉昭雄、広瀬勉、神田英輝• 福里隆一、本田真己、阿尻雅文• Benjamin C. McCoy、J. M. Smith、Artiwan Shotipruk、Maria J. Cocero、Youn-Woo Lee、Feral Temelli、Bushra Al-Duli、Rodolfo Morales、Yaping
Zhao• 名古屋大学＋熊本大学• 博士学位取得者• 佐藤政樹、近藤満、Bhupesh C. Roy、Wahyudiono、Siti Machmudah、斉藤崇、
Ruha Askin、Asli Yuksel、HongTao Wang、岩谷智子、川人紫、川尻聡、田中雅裕、星野宗広、高橋明子、源田稔、山内悟留、Pradip C. Mandal、柴田勝司• 根路銘葉月、中川尚治、林祐衣、星野倫太朗、上森千穂、Chhouk Kimthet、Mardis Mardiansyah、村上和弥• 多くの海外の大学の学位取得者• 博士課程大学院生• 朱力、朱琬莹、胡新、張葉林、星野有理子• 研究費• 科研費補助金、日本学術振興会、
科学技術振興機構、環境省補助金、経済産業省、COEプログラム、
G-COEプログラムなど

• 家族

福里隆一

Siti Machmudah
Wahyudiono

これから株式会社 SCFソリューションズ（4月１日設立）
SCF Solutions Co. Ltd.
p超臨界技術センター株式会社
Super Critical Technology Centre Co. Ltd.
p・・・

Nagoya Industrial Science Research Institute96