The Recent Developments in

the HiGee Technology

Prof. Jian-Feng Chen

Research Center of the Ministry of Education for

High Gravity Engineering & Technology
Beijing University of Chemical Technology,
Beijing, China
Venice, Italy
1
June 14-17, GPE-EPIC 2009
Higee tech. by Chen
 Outline
1. Introduction
2. Fundamentals of HiGee (High Gravity) Technology
¾ Hydrodynamics
¾ Mass transfer
¾ Micromixing

3. Applications of HiGee Technology

- Case Studies
Engineering of Nanoparticles
Reaction Process Intensification
Separation process Intensification

Higee tech. by Chen

Introduction what is PI & what could be beneficial

Process intensification?
Innovation on process
and equipments, lead to:
• reduction of equipment
size dramatically
• reduction of process
units operations

Benefit of PI
Process Industries
• product quality improvement
• energy saving and cost reduction
• resource consumption reduction
• pollution reduced
3
• safety improvement Higee tech. by Chen
 What could PI do?

Energy-oil
Chemical and gas
Industries Environment

Mass, heat transfer

Nanomaterials Mixing and Life Science
Reaction engineering

Process
Intensification

4
Process Industries
Higee tech. by Chen
Example Importance of Micromixing
(mixing at molecular scale)
liquid phases complex and fast reactions

A＋B＝R （instantaneous reaction)

R＋A＝S （fast reaction）
Ratio of reactants：A:B=1：1 (mol)

Chemical reaction：a molecular-scale process

Selectivity：XR－two extremes
• XR=0%
• XR=100%
Classical reaction engineering theory cann’t explain
5
the above case. Why? How?
Higee tech. by Chen
 Micromixing controlled processes
Micromixing
Dominate and control

Fast chemical process（tR<or~ tM)

Reactor Design & Scale-up

Nanomaterials Polymerization Organic

(PSD，Morphology) reaction
（MWD） （selectivity）

Fundamental of Engineering, PI?

6

Higee tech. by Chen

 High Gravity (HiGee) Technology — RPB

Inlet

Rotating
Packed Bed
(RPB)

In 1979, Dr. C. Ramshaw

invented RPB to intensify
mass transfer for G-L
Rotating
separation process
Shaft
- European Patent,
Outlet 7
0002568,1979 Higee tech. by Chen
Our research work

Fundamental
Fast Research
Separation
Reaction Process

Mass, Heat Transfer Reaction

Nanomaterials Mixing and Coupled with
Reaction Engineering Separation

High Gravity
Technology

Process
Intensification

Higee tech. by Chen

Fundamental research

(1) Fluid Flow in RPB

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Visualization of fluid flow in RPB

Liquid flow pattern

Film flow + pore flow Droplet flow

N<600 rpm (15-60g) N>800 rpm (>100g)

10
Guo, Chen, et al., Chem. Eng. Sci., 2000,55:1699-1706
Higee tech. by Chen
 Liquid flow-film thickness
Radius L Speed Liquid film Liquid film thickness
thickness
m m3/h rpm
μm
νL
0.15 1.5 450 17 δ = 4 .20 × 108

af ω 2 R
0.15 1.5 500 16

0.15 1.5 600 14 L — flow volume rate

0.15 1.5 750 11 ω — Angular velocity
R — radius diameter
0.15 1.5 900 4
ν — kinetics viscosity
0.15 1.5 1050 2

Guo K., Chen J. F., et al. Chem. Eng. Sci., 2000, 55:1699-1706 11

Higee tech. by Chen

 Droplet diameter
Speed L Mean diameter
rpm m3/h mm
Mean diameter
1000 1.0 0.111 1
⎛ σ ⎞ 2
1000 1.75 0.140 ⎜
di = B⎜ 2 ⎟⎟
1000 2.5 0.192 ⎝ ω Rρ ⎠

800 1.0 0.204

σ — liquid surface tension
800 1.75 0.203
ω — Angular velocity
800 2.5 0.238 R — radius diameter
ρ — liquid density
600 1.0 0.229

600 1.75 0.253

B = 0.5 - 0.9
600 2.5 0.276
12

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 Residence time distribution in RPB
Electric conductivity probes are mounted on the
rotor, which rotate with the rotor
The signal transformed by electric brushes
In-situ measurement

Typical residence time distribution

inlet

outlet

13
Guo K., Chen J. F., et al. Chem. Eng. Sci., 2000, 55:1699-1706
Higee tech. by Chen
 Typical residence time curves Residence time vs. Liquid flow rate

600rpm
inlet
800rpm

outlet

Residence time vs. gas flow rate Residence time vs. rotating speed

2.0 G=0
L=1.0m3/h

L=2.5m3/h

14

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Fundamental research

(2) Mass transfer in RPB

15

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 Average mass transfer coefficients in different zones

Out of the
rotor
inside the
rotor
Inner edge
of rotor

Mass transfer coefficient Average mass transfer

measured by water deaeration coefficient on two kinds
(liquid phase control) of packing

Packing II

Packing I

16

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Mass transfer modeling of CO2 absorption
I layer I+1 layer I+2 layer I+3 layer Droplets model

c '
e

di

r
c e'

Single drop
Simplify physical model

Based on our visual study, when rotating speed is over 800rpm,

liquids exist mainly in the form of droplets.

17
F. Yi, J.F. Chen, et al., Chem. Eng. J., 145 (2009): 377–384
Higee tech. by Chen
 Modeling of CO2 absorption in RPB
Mass balance in droplet Main assumption
1. Steady-state condition prevails.
2. The amount of water in gas-phase is neglected.
D d ⎛ dc ⎞
L
⎜ R
2
⎟ − k1 (c − ce )= 0 3. The plug-flow condition is applicable to both gas and liquid phases.
R 2
dR ⎝ dR ⎠ 4. The pressure drop in the RPB is neglected.
5. Isothermal absorption takes place in the RPB.
∂ c
= 0
∂ t d ⎛ k1 ⎞ ⎛ k1 d ⎞
c = (c 0 − ce ) s in h ⎜ R ⎟ s in h ⎜ ⎟ + ce
c (d / 2) = c0 2R ⎝ DL ⎠ ⎝ DL 2 ⎠

dc
dR
= 0 +
R=0 dc
k L (c 0 − ce )= D L
dR R = d /2
;

kG R T
(a )
− 2 .0
= 2 R eG S cG1/3 ⎛ k1 ⎛ k1 d ⎞ 2 ⎞
t d
0 .7
p kL = D ⎜⎜ ta n h ⎜ ⎟ − ⎟
atD G L
⎝ DL ⎝ DL 2 ⎠ d ⎟⎠

− 0 .5
Result
H
0 .6 0 .2 2
⎛ ω 2r ⎞ ⎛ u ⎞ ⎛ ν ⎞ 1 1
εL = 0 .0 3 9 ⎜
⎝ g0 ⎠
⎟ ⎜ ⎟
⎝ u0 ⎠
⎜ ⎟
⎝ν 0 ⎠
= +
K G kG k L (concentration of outlet gas)
Gas phase Runge-Kutta method
Absorption rate mass balance
⎛ ⎞
N CO2 = K G a ( P y − ce H ) = K G
6ε L
d
( P y − ce H )
+ G N 2
d ⎜
⎝ 1 −
y
y
⎟ = N
⎠
C O 2
2π rh d r
18

Higee tech. by Chen

 Experimental
Benfield solution (un-promoted) to absorb CO2

⎯⎯
→ OH − + HCO3−
CO32− + H 2O ←⎯
⎯ Instantaneous reaction

⎯⎯⎯
kOH
CO2 + OH − ←⎯⎯ → HCO3−
⎯ Rate-controlling step
k− OH

⎯⎯
→ 2 HCO3−
CO2 + CO32− + H 2O ←⎯
⎯ Total reaction
T
Drain

T
CO2 Analyzer
Flowmeter

T
CO2 Analyzer

Gas Heater

T
Motor Flowmeter Flowmeter

Hot Steam Liquid Tank

Absorbent Tank Pump 19
Liquid Sampling Drain CO2 N2
Higee tech. by Chen
Modeling results vs. experimental results
0.0070

0.0065

0%
+1
0.0060

0.0055
0%
-1
yo,predicted

0.0050

0.0045

0.0040

0.0035

0.0030
0.0030 0.0035 0.0040 0.0045 0.0050 0.0055 0.0060 0.0065 0.0070
yo,experimental

Most of the predicted y0 (mole fraction of CO2 in outlet gas) agreed well
with the experimental data with a deviation within 10% 20

Higee tech. by Chen

Effect of operation parameters on mass transfer coefficient KGa
-4 -4
1.4x10 1.6x10

volumetric mass transfer coefficient(mol Pa m s )

volumetric mass transfer coefficient(mol Pa m s )

-1
-1

-3
-3

1.2x10
-4 79.70 L/h -4 0.920 mol/min

-1
-1

1.4x10
44.28 L/h 0.690 mol/min
N=1300rpm,G=0.481mol/min,t=356K N=1000rpm,L=61.99L/h,T=356K
-4 -4
1.0x10 1.2x10

-5 -4
8.0x10 1.0x10

-5 -5
6.0x10 8.0x10

-5 -5
4.0x10 6.0x10

-5 -5
2.0x10 4.0x10
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
r* r*
Effect of the liquid flow rate on volumetric mass transfer coefficient in RPB Effect of the gas flow rate on volumetric mass transfer coefficient in RPB

volumetric mass transfer coefficient(mol Pa m s )

-4

-1
-4
1.2x10 1.4x10
volumetric mass transfer coefficient(mol Pa m s )

-3
-1
-3

-1
1300 rpm
375 K
-1

1.0x10
-4 1100 rpm 1.2x10
-4

900 rpm 356 K

L=44.28L/h,G=0.481mol/min,T=356K N=1300rpm,L=70.84L/h,G=0.481mol/min
-5 -4
8.0x10 1.0x10

-5
6.0x10 8.0x10
-5

-5
4.0x10 -5
6.0x10

-5
2.0x10 -5
4.0x10
0.0 0.2 0.4 0.6 0.8 1.0
0.0 0.2 0.4 0.6 0.8 1.0
r*
r*
Effect of the rotating speed on volumetric mass transfer coefficient in RPB Effect of the temperature on volumetric mass transfer coefficient in RPB
21
F. Yi, J.-F. Chen, et al., Chem. Eng. J., 145 (2009): 377–384 Higee tech. by Chen
Mass Transfer capacity in various devices

22

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Fundamental research

(3) Micromixing in RPB

23

Higee tech. by Chen

 Experimental setup for micromixing

A+ B ⇔ R
C+B⇔ S
Parallel-Competition Reactions

tM S

tM S
RPB with radial sampling tubes

24
Yang and Chen et al., Ind. Eng. Chem. Res., 2005, 44, 7730
Higee tech. by Chen
Experimental Results -segregation index
iodide-iodate reaction 0 .0 2 6

0 .0 2 4

−
H 2 BO 3 + H + ⇔ H 3 BO 3
0 .0 2 2
N =600rpm a=12 C H + =0.2m ol/L
0 .0 2 0

XS
0 .0 1 8

− − +
5 I + IO 3 + 6 H ⇔ 3I 2 + 3H 2 O 0 .0 1 6

0 .0 1 4

− −
I + I2 ⇔ I3 0 .0 1 2

0 20 40 60 80 100 120
R /m m

0.0130
0.0125
XS at different radial positions
0.0120 a=12 CH+=0.16mol/L
0.0115 N=600 rpm
0.0110 N=1200 rpm
0 .01 4
0.0105
0 .01 3
0.0100
XS

0 .01 2 N = 9 0 0 rp m a = 7 .2 C H + = 0 .1 6 m o l/L
0.0095
0 .01 1 V A = 6 L /m in
0.0090 V A = 9 L /m in
0 .01 0
0.0085
0 .00 9

XS
0.0080 0 .00 8

0.0075 0 .00 7

0.0070 0 .00 6

0 .00 5
0 20 40 60 80 100 120
0 .00 4
R/mm
0 20 40 60 80 1 00 12 0 14 0
R /m m

Effect of rotating speed on XS Effect of liquid flow rate on XS

Higee tech. by Chen
 Micromixing efficiency in RPB - Modeling
1

0.01

1E-4
Micromixing
Xs
1E-6 characteristic time
1E-8
estimated
1E-10
1E-12 1E-11 1E-10 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1

τM =0.1 ms
τm/s

0.1

Xs
0.01

c.f, in conventional
1E-3 stirred tank

τM =5-50ms
1E-5 1E-4 1E-3
τm/s

Relationship of XS and tm in our experimental

condition

Yang and Chen et al., Ind. Eng. Chem. Res., 2005, 44, 7730
26

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 Summary (fundamental)
Two unique advantages: most intensified mass transfer and
micromixing in RPB

27

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 Application Fields of HiGee Technology

Micromixing controlled processes

Nanoparticle Syntheses Fast reaction polymerization

Mass-Transfer limited processes

CO2 H2S/CO2 Deoxygenation of Water SO2 Dedusting

28

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 Application I:

Nanoparticles Syntheses
— Engineering of Nanoparticles

29

Higee tech. by Chen

Nanoparticles – building block for nano-system
Nano -catalysts
Nano-catalysts Nanoparticles
Nanoparticles Nano
Nano-- electrode
electrode
for
for Chem.
Chem. Ind.
Ind. for
for IT
IT for
for energy
energy

MLCC capacitor

Medical
Medical nano
nano-- Drug
Drug nanoparticles
nanoparticles
device
device for
for Inhalation
Inhalation

纳米金探针免疫检测技术的特点：

快速、准确、方便，应用面广泛。

吸水纸
控制线
测试线
显色区

背板
胶
金膜
上样区

30
• Materials in particles form > 70%
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Mechanism

Process of particle formation

How to
Engineer the
nanoparticles
with cost
effective
way?

31
J. Rieger, & D. Horn, Angew. Chem. Int. Ed., 2001, 40, 4330 -4361 Higee tech. by Chen
 Reactive precipitation

Poor
M mixing

L
K Good
mixing
In
In conventional
conventional stirred
stirred tank
tank

Problem：
τM = 5 ~ 50ms， τ = 1ms；
τM > τ — in micromixing
control zone

Three different distribution Difficulties in control

PSD, scale-up effect
J.F. Chen et al., Chem. Eng. Sci., 51,1957-1966, 32
1996 Higee tech. by Chen
 Engineering of nanoparticles — Micromixing
Requirements
Intensified micromixing
= uniform PSD + nano-sized
& mass transfer

Mechanism

A+B→P
Nucleation rate:
dN / dt = K N ( c P − c * ) a ,
a = 5 ~ 18
Crystal growth rate:
dl / dt = kG (cP − c* )b ,
b =1~ 3
33
Higee tech. by Chen
 Principles for precipitator design

Micromixing
Micromixing Nucleation
Nucleation
characteristic time ττM
characteristic time M
characteristic time ττ
characteristic time

⎛υ ⎞ 6d n
1/ 2 2 *
τM = k⎜ ⎟ τ=
⎝ε ⎠ D ln S

Principles
Principles

When τM < τ, ideal reactor for fast reaction process, easy

to control (ideal environment）
When τM > τ, non-uniform environment，difficult to
control（non-ideal environment）

34
Higee tech. by Chen
 High Gravity Technology — RPB

Inlet

Rotating Packed Bed

(innovation design)

Rotating Shaft
Liquid Outlet
τM < τ
τM=0.1ms Ideal reactor for nanoparticles synthesis
τ =1ms 35
Higee tech. by Chen
Particle size and morphology control of nanoparticles

Particle size Morphology

control control

CO2 ＋ Ca(OH)2= CaCO3 + H2O

36
L=0.3m3/h
34
G=0.42m3/h
32 cA0=73kg/m3
dp (nm)

30
28 needle spindly
26
24
22
0 1000 2000 3000
2
gr (m/s )

Effect of high gravity level on

particle size
Cubic flaky
36
Higee tech. by Chen
Comparison of PSD of cubic CaCO3 prepared by HGRP
and commercial product

50
45
40 Prepared by

Frequency density (%)

35
30 HGRP
25
20
15
10
5
30nm
0
0 10 20 30 40 50
narrow distribution
Par ticle s ize (nm )

30.0 Commercial
25.0 product
Frequency density (%)

20.0
by conventional
15.0

10.0

5.0
75nm
0.0
wide distribution
0 25 50 75 100 125 150
Particle size (nm )
37
Higee tech. by Chen
 From idea to commercialization
Nanoparticles production by High Gravity Technology

40 t/a 10000t/a
• 1997，40 t/a
• 2000，3000t/a
• 2001，10000t/a
• Price: €400 /ton

Volume / Carbonation Mean Production

Scale Variance
batch time size capacity
(m3) (min) (nm) (t/a)
Bench 3 12~20 25~36 0.22~0.38 4.7
Mini-
80 20~25 15~30 0.15~0.27 110
Pilot
Full
2800 22.5 30 0.23 4000
scale
30nm
No scale-up effect ! 38
Higee tech. by Chen
 Application of nanoparticles - nanocomposite
Inorganic Nanoparticles → Dispersion → Formulation
→ Processing → End products

Raw In polymer Well Dispersed in Increased

materials 450 %
matrix polymer matrix 90
80

Impact strength, KJ/m2

70
Master batch
60
50
40 Direct
30 addition
20
10
0 2 4 6 8
Nanoparticles (PHR)
100nm 250nm 250nm
Polymer nanocomposites
Invention: Core-shell particles technique
Mixing in master batch
preparation method
Effect:
High content of inorganic nano-particles in the master batch (75％)
Nano-dispersion was reached, mechanical property increased significantly 39

Higee tech. by Chen

Applications
PP nanocomposite for bumper
Beijing Yanshan Petrochemical Corp. (Sinopec)
item Unit Original PP increase
PP nanocomposite （%）
(Audi)
Charpy noched impact 23℃ KJ/m2 67.0 81.4 21. 4 Both
Both impact
impact
strengrh
-20℃ KJ/m2 12.0 30.1 150 strength
strength and
and
Flexural modulus MPa 763 909 30. 0 flexural
flexural
Flexural strength 23℃ MPa 17.0 18.8 10. 6
modulus
modulus are
are
increased
increased
-40℃ MPa 48.2 74.8 55. 2
remarkably
remarkably
Tensile yield strength MPa 15.7 16.2 3. 2

Elongation at break % 530 613 15. 7

Melting index g/10min 8.3 12.9 55. 4

40
Higee tech. by Chen
Applications
Applications of Rubber nanocomposites
Nanocomposites for sole of Nanocomposites
Nanocomposites for
for
of
adidas shoes latex gloves
500％tensile modulus is
increased 112％
(5％-7.5％ CaCO3
nanoparticles)

Nanocomposites
Nanocomposites forfor
• Raising the silicone sealant
performance of UV Tensile strength is
anti-ageing resistance 50% higher than
Japanese products,
• Improving the and 80% higher
additives dispersion in than home-made
shoes matrix China-Baiyun Company products
41
Higee tech. by Chen
Applications
Nano-coating for paper
Mechanical Gurley stiffness of paper is increased by
Property 47.9%

200
ƒ Adding starch
ƒ Adding 1μm CaCO3 particles 176
168
ƒ Adding 40nm CaCO3 nanocomposites
mg
挺度，mg

160
139 141 137
Gurley挺度，

130 132
119 120 124
120 117
横向Gurley

80
横向

40

0
0 15 40 80 100 150
钙基纳米粒子添加量，lbs/T Paper
配方— 纤维： 60 lbs/3300 sqft paper；淀粉：80 lbs starch/T paper

By Weyerhaeuser
Company, USA
42
Higee tech. by Chen
 Monodispersed nanoparticles dispersion
nano Cu / Oil Nano metal oxide
(cooperation with NanoMaterials
• 2-8nm (5nm) Technology Pte. Ltd., Singapore)

• Cu in oil : 15% Good transparency

• Transparent、stable
• Capacity: 100t/a 53% 48% 43% 39% 35% 24%

Nano CaCO33 / Oil

• 10nm
• Solid in oil: 30%
• Transparent、stable
• Production capacity: Low
1000t/a
Solid content
100nm (disperse medium = organic solvent)

Patents：ZL200410037885.9 ; 200610165009.3 43
Higee tech. by Chen
Potential Applications

magnetic fluid

E-paper E cosmetics
D F

rubber
C Mono- G
dispersed drug
nano-
particles
lubricating oil B H

A I glass

chemical fiber etc

……
paint 44
plastic Higee tech. by Chen
 ZnO/PMMA-PS nanocomposites

ZnO in MEK 5% 10% 20% 30% 40% 50%

√ √
100

10nm
80
blank
1%
2%
60 5%
10%
ZnO/PMMA-PS film

T%
20%
40 30%
40%
20
50%

9nm 0
200 300 400 500 600 700 800
wavelength/nm

The visible transmittance of the film is less than

1% with 10% ZnO, while the film has the same
20nm transparence as the sample without ZnO. 45
Higee tech. by Chen
 ZnO/polycarbonate nanocomposites
SEM 100
ZnO in MEK ZnO/PC film
80
blank
60 1%

T(%)
2%
40 5%
12%
20
20%
0
10nm 200 300 400 500 600 700 800

wavelength(nm)
ZnO/PC＝12% Trasmittance of ZnO/PC nanocomposites
with different ZnO content

100

80

60
T(%)

40 ZnO/PC film
GE-PC-223R
20

0
200 300 400 500 600 700 800
wavelength(nm)

Trasmittance of ZnO/PC compared with that of UV-

blocking PC film from US commercial source ZnO/PC film US PC-223R 46
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ZnO/acrylic polyurethane nanocomposites

ZnO in EtAc 100

80

0%
60
3%

T%
5%
8%
40

20

10nm
0
200 300 400 500 600 700 800
wavelength(nm)

Trasmittance of ZnO/AC-PU nanocomposites

SEM (ZnO/AC-PU film) with different ZnO content
ZnO/AC-PU＝5%

ZnO/AC-PU Blank

47
Higee tech. by Chen
background
Future of drug nanoparticles

Poor-water-soluble drugs: enhancing solubility and

dissolution rates of solid oral formulations

• Nernst-Noyes-Whitney equation:

dC DS (Cs − Ct ) dC
= d S
dt Vδ dt
dC
— dissolution rate；C — solubility；
dt
S — specific surface area

• Pulmonary delivery inhaled drug: realizing the

deep lung deposition to increase the efficiency
Particle Size: < 500-2000 nm

Potential worldwide market: 480 B USD, 50% share made by

nanotechnology (NNI, 2000, USA)
48
Higee tech. by Chen
Drugs Nanoparticles prepared by Higee Technology
Anticancer drug Antiasthma drug

Adrenal corticosteroid Antibiotic drug

Lipid-lowering drug Immunization drug Antihyperlipemia drug Hepatoprotective drug

49
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 Application II :

Fast Reactions
Intensification of micromixing &
mass transfer limited reactions

50

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Application II — Fast Reactions

(1) Polymerization
- Isobutylene Isoprene Rubber (IIR)

51

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Cationic polymerization -micromixing limited

Synthesis of IIR

CH3 CH3
IB CH2 = C IP
CH2 = C－CH=CH2
CH3

• Fast reaction(< 1s)

• low temperature
• high exothermic
Cationic Polymerization

CH3 CH3 CH3

IIR CH2 C
m
CH2－C = CH－CH2 l
CH2 C
n

CH3 CH3

52

Higee tech. by Chen

 RPB for IIR synthesis – new process
Chain-growth in polymerization is first-order reaction, the
characteristic reaction time is

t1/ 2 = ln 2 0.01~0.1 ms
kp

Conventional stirred tank

reactor RPB
tm 5~50 ms 0.1~0.01 ms

tm > t1/ 2 Nonhomogeneous micro-environment

Choose RPB
tm ≤ t1/ 2 Homogeneous micro-environment

53

Higee tech. by Chen

 Experimental setup
RPB process for Polymerization of IIR

Flow chart of Polymerization of IIR

1-N2 cylinder; 2-refrigerant tank； 3-isobutene,isoprene and dichloromethane tank; 4-aluminium
chloride and dichloromethane tank; 5-metering pump; 6-RPB; 7-IIR tank
54
RPB size (rotator):Do=258mm, DI=150mm, H=50mm
Higee tech. by Chen
Effect of rotating speed on MWD in RPB

Mw/Mn N
3.0
-1
2.72 600r· min
Mn× 10-5

2.7
-1
2.13 900r· min
2.4

2.1 1.99 1200r· min

-1

1.8
-1
1.93 1500r· min
1.5
600 900 1200 1500 10 15 20 25
N/r· min-1 Elution time/min

TP NL U1 IB IP [AlCl3] VR
N≥1200 r·min-1
173 45 2.36 2.7 0.05 0.011 10
55

Higee tech. by Chen

Effect of packing thickness on MWD in RPB

Mw/Mn NL
3.0 2.34 10

2.5
Mn× 10-5

2.26 20
2.0

1.5 1.99 45
193K
183K
1.0
173K
1.96 60
0.5
10 20 30 40 50 60
NL
10 15 20 25
packing layer Elution time/min

NL≥45 N U1 IB IP [AlCl3] VR
1200 2.36 2.7 0.05 0.011 10
56

Higee tech. by Chen

Modeling and experiment results of IIR polymerization
Calculation
Calculation of
of mean
mean
Polymerization
Polymerization of
of IIR
IIR molecular
molecular weight
weight
Chain-initiation: W ∑n M i i

I + LA
+
I LA − Mn = = i

n ∑n i
I + LA − + M 1 ⎯⎯→
ki
P1+ LA − i

Chain-growth: ∑ ([C ] × M
i WC i ) + ∑ ([E i ] × M WE ) + [A] × M WA
i
+ −
P LA + M 1 ⎯ ⎯
k p, M 1
⎯→ P + −
= 2× i i

[A] + ∑ [E i ]
n 1(n + 1) LA
+ − k P, M 2 + −
P LA + M 2 ⎯ ⎯⎯→ P
n 2(n + 1) LA i

Chain-transfer: 3.0
k tr,M1
Pn+ LA − + M1 ⎯⎯
⎯→ Pn1 + P1+ LA −
2.5
Chain-termination:

Mn× 10-5
k
P n+ LA −
P n2 + LA 2.0
t

Reaction characteristics: 1.5

Experimental (Tp)
193K
1、very low reaction temperature 1.0 183K
173K
2、 reaction time < 1s 0.5
Simulation

0.0 0.2 0.4 0.6 0.8 1.0

3、activation energy < 0 r*

57
• Chen J.F., Gao H., Zou H.K., Chu G.W., et al., AIChE J. (2009, Accepted)
Higee tech. by Chen
Comparison of Higee polymerization with
conventional technology
Parameters Conventional RPB
Temperature（K） 173~177 173~193
Residence time（s） 1800~3600 <1
Operation cycle（h） 24~60 2~3
Material flow velocity(m·s-1) 4~7 2~3
Material circulation YES NO
Isobutene density（%，V） 30~35 15~25
Isoprene density（%，V） 2.5~3 2~3
Operation pressure（KPa） 240~380 100
Product number average molecular
≥1.5 1~3
weight（×105）
Product molecular weight distribution index 2.5~3.1 2~2.7

58

Higee tech. by Chen

Application II — Fast Reactions

(2) MDI production

59

Higee tech. by Chen

 Applications of MDI

¾ MDI - diphenylmethane diisocyanate products

¾ MDI is the most important raw material in polyurethane
(about 50%) energy
¾ Polyurethane ranks the fifth in world's plastic production conservation
¾ Excellent heat insulation, elasticity, abrasion resistance and
oil resistance properties of polyurethane

Submarines'and
Refrigerator armored vehicles'
Sofa seat freezer Auto materials coating

The rockets'
insulation

shoemaking Olympic Qinghai-tibet Spandex

Venues railway
embankment 60

Higee tech. by Chen

Condensation reaction –key process in MDI production

Condensation
reaction NH2
HCl
+ HCHO NH CH 2 NH CH 2 NH2
n
Interconversion
reaction

H
E
A
T
NH CH2 NH CH2 NH2 H2N CH2 NH2
n n
NH2
Reaction characteristics: - micromixing controlled
1.Condensation reaction is rapid, strongly exothermic, complex reactions
2.Formaldehyde is poorly dispersed for the high viscosity. Many by-products are
easily generated (such as 2-methylaniline, n-methyl composites, etc.), which
affect the quality of target product, and even block the pipeline (trouble)
3. Effective dispersion and temperature control of formaldehyde are very
important to improving the quality of polyamines .

Challenges : Demand for fast molecular mixing

61
H. Zhao, J.F. Chen et al., Chem. Eng. J. 2009, in press. Higee tech. by Chen
 Commercial application of innovative HiGee
reactors for MDI production

Industrialized units

Benefit: capacity increased 50%, from 160K to 240K t/a, energy saving about 20%,
impurity content reduced by 30%, blocking problem solved 62

Higee tech. by Chen

 Application II — Fast Reactions

(3) Reaction coupled with separation

process
Case — Hypochlorous Acid Production
(mass transfer limited)

63

Higee tech. by Chen

 Industrial application
－ Hypochlorous acid production by Dow Chemical Co

Reaction: HOCl (g) (fast desorption）

Cl2 (g) + NaOH (l) = NaCl (l) + HOCl (l) （target product，fast reation）
2HOCl (l) +2NaOH(l) = NaClO (l) +NaCl＋H2O (side reaction，fast）
DOW Cooperated with our group, we
provided engineering design fundamentals of
RPB (such as liquid distributor, pressure
drop and equipment dimension, etc.),
developed the industrial technology of
hypochlorous acid production with high
gravity reaction and separation method.
Benefit:
HClO yield increased by 10%
equipment investment saved by 70%
Cl2 recycle volume reduced 50% 64
(In courtesy of DOW Chemical Co.)
Higee tech. by Chen
 Application III :

Separation processes

65

Higee tech. by Chen

Application III — Separation processes

(1) Deoxygenation of Water

66

Higee tech. by Chen

Deoxygenation of oilfield feeding water
Oxygen content required in
oilfield
Feeding water: ＜50ppb
Conventional method:
vacuum packed tower,
single or two stages, large
equipment volume and high
investment, oxygen content＞
100ppb, chemical treatment
needed to further remove O2
Higee technology has obvious
advantages over conventional
ones
Particularly suitable for Conventional technology:
offshore oil platform vacuum packed tower 67

Higee tech. by Chen

 Deaeration of water-
Sinopec,China separation by HiGee
O2: inlet 6-12 ppm Capacity:250t/h
outlet ＜50ppb

Overview of No. 2 Central Platform in Chengdao,

Chengdao,
Shengli Oilfield, China

The first known example of its（RPB’s） commercial

use was reported in 1997 by Shengli Oil Field in
China, where 1.5-m-dia. rotating strippers replaced
30-m-high vacuum towers for the deaeration of
water….
－ USA Scientists from Oak Ridge National lab, 68
Chem. Eng. Prog., 90(10):50, (2003)
Higee tech. by Chen
 Vacuum Higee
deoxygenation deoxygenation
Oxygen in water
6~12 6~12
supply
200~800ppb
Oxygen in water after (single tower)
50ppb
treatment 50~200ppb
(two towers in series)
Ground space 1 0.4
Land requirement 1 0.6
Equipment weight 1 0.2
Equipment height 1 0.25
Investment 1 0.6
Power consumption 1 <1 69

Higee tech. by Chen

Application III — Separation processes

(2) Flue Gas Treatment

(desulfurization)

70

Higee tech. by Chen

 Design data basis
(Fujiang Petroleum Refinery Co.)

Gas to be treated
feeding rate: 11 t/h, t = 40°C , p = 1.1Mpa.
Composition of dry gas：H2S ≤ 2.27% CO2 ≤ 3.72%

Absorption solution - recycled deficient amine solution:

Composition: H2S ≤ 1.0wt% CO2 ≤ 0.5wt%
Amine solution flow rate: 13-16 t/h, t = 40°C , p = 1.1Mpa.

Requirement: Gas after desulfurization: H2S ≤ 20mg/NM3

Reactive absorption:
2HOC2H2-NH2 + H2S = (HO-C2H4-NH3)2S=2HOC2H4-NH3HS
71

Higee tech. by Chen

 H=33m
D=1.2 m
Hpacking=12m
D=1.2 m Vpacking=14m3
H=1.42m
Rotor:
Di=0.35m
Do=0.9m

Original
RPB Absorption
Tower

72

Higee tech. by Chen

 Desulfurization effects of RPB vs. conventional PBT
2500 •X: days of experiment; Y: outlet H2S index (ppm)
2000
1500
1000
500
0
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65

0~2 3~22 23~27 28~43 44~

Without with RPB turn on stop RPB again
RPB RPB again
low and steady H2S index
high
H2S index, meet H2S index increased again
H2S requirement reduced again
index
stop RPB
73
unstable and high H2S index
Higee tech. by Chen
Application to fertilizer plant

Benefit: absorption
solution recycle
volume reduced by
50%
74

Higee tech. by Chen

Application III — Separation processes

(3) Polymer devolatilization

75

Higee tech. by Chen

Polymer devolatilization by HiGee

Content of Volatile, wt%

0.5

0.4 97.5%
0.3

0.2

0.1

0.0
400 600 800 1000 1200 1400
Rotating speed, rpm

Pressure Efficiency/%
Equipment Time
/Pa single twin
2300 20 min 86 92
HiGee
666 20 min 90 99.2
3300 10 h 2
Stirring Tank
550 10 h 92

76
Chinese Patent: J. F. Chen, et al., 200710120712.7 (2007)
Higee tech. by Chen
Summary Inorganic

metal
Desulfuri Nano
-zation particles drug
deaeration

HiGee
Separation
PI
Techn. Polymerization
platform
CO2
Reaction
capture
devolatili
HOCl
PI
zation

sulfonation
MDI
77

Higee tech. by Chen

 Conclusions
¾ HiGee can tremendously intensify
micromixing and mass transfer
¾ HiGee is a cutting-edge technology platform
for process intensification, including
nanoparticles syntheses, reaction,
separation, mixing, emulsification
¾ HiGee technology is ready for industrial
innovation of chemical processes limited by
micromixing and mass transfer

78

Higee tech. by Chen

 Acknowledgements
My colleagues & students :
Prof. K. Guo, Prof. F. Guo……
My government:
¾ National “973” Plan
¾ National “863” Plan
¾ National Key Development Plan
¾ NSF of China
My sponsors from industries:
¾ Enping Chemical Co., China
¾ Yantai Wanhua Co., China
¾ Fujiang Petroleum Refinery Co.,
Sinopec, China
¾ CNPC, China Petroleum
Cooperation,…
¾ Nanomaterials Technology Pte. Ltd.,
Singapore
¾ DOW Chemicals Co., USA
¾ BASF AG., Germany
¾ Dow Corning Co. USA

79

Higee tech. by Chen

 Welcome to visit Beijing (China)

The Bird's Nest and The Water Cube

80

Higee tech. by Chen

 Thank you for your attention!

Contact: chenjf@mail.buct.edu.cn

Higee tech. by Chen