Industrial Chemistry Library, Volume 9

High Pressure Process Technology:
Fundamentals and Applications

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Industrial Chemistry Library
Advisory Editor: S.T. Sie, Faculty of Chemical Technology and Materials Science
Delft University of Technology, Delft, The Netherlands

Volume 1

Progress in C 1 Chemistry in Japan
(Edited by the Research Association for C 1 Chemistry)

Volume 2

Calcium Magnesium Acetate. An Emerging Bulk Chemical for
Environmental Applications
(Edited by D.L. Wise, Y.A. Levendis and M. Metghalchi)

Volume 3

Advances in Organobromine Chemistry I
(Edited by J.-R. Desmurs and B. G6rard)

Volume 4

Technology of Corn Wet Milling and Associated Processes
(by P.H. B lanchard)

Volume 5

Lithium Batteries. New Materials, Developments and Perspectives
(Edited by G. Pistoia)

Volume 6

Industrial Chemicals. Their Characteristics and Development
(by G. Agam)

Volume 7

Advances in Organobromine Chemistry II
(Edited by J.-R. Desmurs, B. G6rard and M.J. Goldstein)

Volume 8

The Roots of Organic Development
(Edited by J.-R. Desmurs and S. Ratton)

Volume 9

High Pressure Process Technology: Fundamentals and Applications
(Edited by A. Bertucco and G. Vetter)

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Industrial Chemistry Library, Volume 9

High Pressure Process Technology:
Fundamentals and Applications
Edited by

A. Bertucco

Universitgt di Padova, DIPIC- Department of Chemical Engineering,
Via F. Marzolo 9, 1-35131 Padova PD, ltaly
G.

Vetter

Universitdt Erlangen-Ni~rnberg, Department of Process Technology and
Machinery, Cauerstrasse 4, D-91058 Erlangen, Germany

2001
ELSEVIER

Amsterdam -

London - New York-

Oxford - Paris - Shannon - Tokyo

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PREFACE

The application of elevated pressures in the manufacture of high technology products is
permanently extending and offering new opportunities. Nowadays this is true not only for
reactions and separations during chemical processing, but also for other production activities
such as jet-cutting, homogenization, micronization, pressing, plastification, spray-drying and
for physico-biological treatments such as pasteurization, sterilization and coagulation. At the
dawn of the new century, it is quite evident that high pressure technology is one of the
emerging tools and methods for improving product quality, both from the economic and the
environmental viewpoints, and for the development of more sustainable processes and

products for the future generations.
Although the development of classical high pressure production dates back to the 1920s
and 1930s (ammonia, low-density polyethylene, synthetic diamonds, etc.), research in this
field has been particularly active in the last twenty-five years, leading to a number of new
opportunities expanding to areas such as materials science and microbiology, and to the bulk
production of foods, pharmaceuticals, cosmetics, and other products. This is also due to the
exploitation of the properties of fluids at the supercritical state, especially supercritical water
and supercritical carbon dioxide, which are expected within a few years to offer alternatives to
organic solvents in many widespread applications.
On the other hand, high pressure technology is usually regarded as a highly specific field,
to which little space is devoted within scientific and technical curricula throughout the world,
so that a "high-pressure culture" is not widespread and the related expertise is difficult to find,
even among physicists, chemists and chemical engineers. In addition, the fear of dealing with
high pressures in production plants always appears as a major issue, and therefore
dissemination of the related knowledge and expertise among the manufacturing community
deserves maximum attention.
Of course, visions for and problems with the application of high pressure have been
discussed and promoted by national and international working groups, both in Europe and
overseas, for many years. Within the European Federation of Chemical Engineering the
working party on High Pressure Technology, now in its second decade and comprising
members from twelve European countries, has developed initiatives for the transfer of
scientific and technological knowledge in an outstandingly efficient manner.
In Europe, one important pillar of these activities is represented by the institution of an
Intensive Course on High Pressure Technology offered annually to European post-graduate
students and funded by the European Union within the framework of the Socrates
Programme. The course has now been rotating for several years between major European
universities. Most of the working party members as well as other experts have contributed
lectures, discussions and class-work problems as well as final examinations. From the
beginning of the course programme the firm intention was to publish the high-level teaching
and educational documentation as a book for a larger community of users, and we are pleased

to present this work now.
A special effort was made to organize and present the matter in such a way that a larger
group of readers and experts can take advantage of it. The book is intended to provide a
comprehensive approach to the subject, so that it can be interesting not only for specialists,

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vi
such as mechanical and chemical engineers, but also beginners with high-pressures who
would like to apply this kind of technology, but somehow are afraid of dealing with it either
on a research- or production s c a l e - biologists, chemists, environmental engineers, food
technologists, material scientists, pharmacists, physicists, and others.
The content of the book, structured into nine chapters, each being sub-divided into a
number of sections, results from the long-term course presentations and the many connected
discussions.
In the first Chapter an overview of the general topic is presented. The motivations of using
high pressure today are summarized and a number of examples provided which relate to highpressure production processes applied currently.
Chapter Two deals with the basic concepts of high-pressure thermodynamic and phase
equilibrium calculations. Experimental methods and theoretical modelling are described
briefly in order to give both a comprehensive view of the problems, and suggestions and
references to more detailed treatments.
The problem of the evaluation of kinetic properties is addressed in Chapter Three,
including both chemical and physical kinetic phenomena.
Then, in the Fourth Chapter the design and construction of high pressure equipment is
considered, with reference to research and pilot units, and production plants as well. This is a
very important part of the book, as it clearly shows that running high pressure apparatus is
neither difficult nor hazardous, provided some well established criteria are followed both
during design and operation.
Industrial reaction units are discussed in Chapter Five, where all the main issues related to

catalytic reactors are discussed, and a special emphasis is paid to polymeric reactors.
The problems connected-with separation processes, units, and equipment are treated in the
Sixth Chapter, focusing the reader's attention on high-pressure distillation and on dense-gas
extraction from solids and liquids.
Relevant safety issues arising in the design and operation of high-pressure plants are
addressed in Chapter Seven. After a general section where testing procedures, safe plant
operation, and inspection are summarized, two examples are dealt with in detail: dense-gas
extraction units and polymerization reactors.
Chapter Eight is concerned with a major question connected with the development of high
pressure technologies in the process and chemical industry, i.e., the economic evaluation of
production carried out at high pressures. In this case, also, the matter is discussed in relation
to three important examples: dense gas extraction, polymerization and supercritical antisolvent precipitation processes.
Finally, Chapter Nine is a collection of currently used and (mostly) potential applications.
Even though it cannot cover all possibilities and ideas put forward continuously by
researchers and companies, the proposed examples provide a thorough view of the
opportunities offered by the extensive use of high pressure technology in many fields.
The book, written by experts in high pressure technology, is intended to act as a guide for
those who are planning, designing, researching, developing, building and operating high
pressure processes, plants and components. The large number of references included will
support the efficient transfer of the actual state of our knowledge. The examples and
problems, which illustrate the numerical application of the formulas and the diagrams, will
provide the reader with helpful tools for becoming acquainted with high-pressure technology.

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~

VII


We would like to thank all the contributors for their excellent co-operation, and Elsevier
for their support during the editing procedure and for the readiness to publish the book. A
special acknowledgement is devoted to Ing. Monica Daminato for her full commitment and
precious help during the final editing of the manuscript and preparation of the camera-ready
copy.
The editors hope that the book will be well accepted and that it will help to promote the
further development of high-pressure technology in the future.
April 2001
Alberto Bertucco
University of Padova

Gerhard Vetter
University of Erlangen-Ntirnberg

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ix

CONTENTS

Preface
Contents

ix


List of Contributors

xxi

lo

Introduction

1

1.1

High pressure definitions and examples in nature

2

1.2

Early historical roots of high pressure technology

2

1.3

High pressure technology today - motivations for using high pressure

3

1.4


High pressure technology today- application survey and examples

4

References

15

Thermodynamic properties at high pressure

17

2.1

Introduction

18

2.2
2.2.1
2.2.1.1
2.2.1.2
2.2.1.3
2.2.2
2.2.2.1
2.2.2.2

Phase equilibria
Principles of phase equilibria

The Chemical potential and the phase rule of Gibbs
Fugacity and activity
Critical phenomena
Classification of phase equilibria
Fluid phase equilibria
Phase equilibria with the presence of solid phases

18
18
18
19
21
24
26
31

2.3
2.3.1
2.3.2
2.3.2.1
2.3.2.2
2.3.3
2.3.4
2.3.4.1

Calculation of high-pressure phase equilibria
Bubble point-, dew point- and flash calculations
Equations of state
Cubic equations of state
Non-cubic equations of state

Solubility of solids in Supercritical Fluids
Polymer systems
Glassy polymers

34
35
39
40
45
46
49
51

2.4
2.4.1

Chemical reaction equilibria
Homogeneous gas reactions

53
55

o

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2.4.2

Heterogeneous reactions


2.5

Experimental methods

57

2.5.1

Vapour-Liquid equilibria

58

2.5.2

Equilibria involving solids

59

56

References

60

Kinetic properties at high pressure

65

3.1


Interesting features at high pressure

66

3.2

Kinetics of high-pressure reactions

67

Molecular theory of reaction rate constants
3.2.2
Activation volume
3.2.2.1 Terms contributing to AVR~
3.2.2.2 Terms contributing to Avs#

67
70
70
71

.

3.2.1

3.2.3
3.2.3.1
3.2.3.2
3.2.3.3

3.2.3.4
3.2.3.5
3.2.3.6

Evaluation of the activation volume from experimental data
Single homogeneous reactions
Parallel reactions
Reactions in series
Chain reactions
Heterogeneous catalytic reactions
Reactions influenced by mass transport

72
72
73
73
74
75
77

3.2.4

Prediction of the activation volume

78

3.2.5
3.2.6

Activation volume as a tool for the elucidation of reaction mechanism

Change of reaction rate constant with pressure

79
80

3.2.7

Problems

81

3.3

Measurement of chemical kinetic data at high pressure

82

3.3.1

Measurement of reaction rates

82

3.3.2

Examples

87

References of sections 3.1, 3.2, 3.3


91

3.4

Transport properties

92

3.4.1

Fundamentals

92

3.4.2
3.4.2.1
3.4.2.2
3.4.2.3
3.4.2.4
3.4.2.5

Estimation of transport properties
Viscosity
Diffusivity in dense gases
Binary diffusivity data in different media
Thermal conductivity
Surface tension

97

97
100
100
102
104

3.4.3

Heat transfer mechanisms in dense fluids: calculation of heat-transfer
coefficients in different arrangements
Single phase convective heat transfer

106
106

3.4.3.1

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xi
3.4.3.2
3.4.3.3
3.4.3.4
3.4.4
3.4.4.1
3.4.4.2

Condensation
Boiling

Overall heat-transfer coefficient for exchangers
Mass transfer mechanisms in dense fluids
External mass transfer
Internal mass transfer

110
112
113
114
114
123

3.4.5
3.4.6

Mass transfer models
Numerical examples

126
133

References of section 3.4
0

139

Design and construction of high pressure
equipment for research and production
High pressure machinery
Requirements and design concepts

Generation of pressure with pumps and compressors

4.1
4.1.1
4.1.2
4.1.3
4.1.3.1
4.1.3.2
4.1.3.3

Pumps
Reciprocating displacement pumps
Rotary displacement pumps
Centrifugal pumps

4.1.4
4.1.4.1
4.1.4.2
4.1.5
4.1.5.1
4.1.5.2

Compressors
Piston compressors
Turbo compressors
Special problems involving high-pressure machinery
Strength of the components
Seals

High-pressure piping equipment

4.2
4.2.1
Tubing and fittings
Isolation and control valves
4.2.2
4.2.3
Safety valves and other devices
References of sections 4.1 and 4.2
4.2
4.3.1
4.3.1.1
4.3.1.2
4.3.1.3
4.3.1.4
4.3.2
4.3.2.1
4.3.2.2
4.3.2.3

141
142
142
143
147
148
155
157
163
164
169

172
172
180
190
190
195
198
199

High-pressure vessels and other components
Calculation of vessels and components
The hollow cylinder under static loading
Strengthening the thick-walled hollow cylinder under static loading
Influence of temperature gradients on design
End pieces side-holes and surface influence

201
201
203
206
210
211

Materials
Typical materials for apparatus and other equipment
Corrosion-resisting materials
H2-attack at elevated temperatures: Nelson diagram

213
213

214
215

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xn

4.3.2.4 Corrosion by carbon monoxide
4.3.2.5 Nitriding by ammonia

215
216

4.3.3
4.3.3.1
4.3.3.2
4.3.3.3
4.3.3.4
4.3.3.5

Vessels and other apparatus
Thick-walled vessels
Multiwall vessels
Closures and sealings
Design details - corrosion-protecting of inner surfaces
Heat exchangers and others

216
216

218
221
223
226

4.3.4
4.3.4.1
4.3.4.2
4.3.4.3
4.3.4.4

Laboratory-scale units
Reactors
Optical cells
Other devices
Small-scale high-pressure plants

228
228
230
233
234

4.4

Instrumentation of high pressure facilities

235

4.4.1


Pressure measurement

235

4.4.2

Temperature measurement

237

4.4.3

Flow measurement

238

4.4.4

Level measurement

240

References of sections 4.3 and 4.4

241

Industrial reaction units

243


Reactors for homogeneous reactions
Polymerization of ethylene

244
244

,

5.1
5.1.1
5.1.2

Tubular reactor

248

5.1.3

Autoclave reactors

250

5.1.4

Conclusions

253
253


References
5.2

Hydrodynamics and mass transfer in fixed-bed gas-liquid-solid reactors
operating at high pressure

Countercurrent gas-liquid flow in solid fixed-bed columns
5.2.1
5.2.1.1 Hydrodynamics in countercurrent fixed beds
5.2.1.2 Mass transfer in countercurrent fixed beds
5.2.2
5.2.2.1
5.2.2.2
5.2.2.3
5.2.2.4
5.2.2.5
5.2.2.6

Cocurrent gas-liquid downflow fixed-bed reactors"
Trickle-Bed Reactors (TBR)
Flow regimes
Flow charts
Models for the hydrodynamics of TBR
Two-phase pressure drop
Liquid hold-up
Gas-liquid interfacial area

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255

255
256
257
257
261
262
265
274
282
288


Xllll

5.2.2.7
5.2.2.8
5.2.3
5.2.3.1
5.2.3.2
5.2.3.3

Liquid-side mass-transfer coefficient
Gas-side mass-transfer coefficient
Some examples of industrial applications of gas-liquid-solid fixed beds
Hydrodesulfurization process
Hydro-isomerization selective hydrogenation
Manufacture ofcyclohexane

5.2.4


Conclusion

299

References
5.3
5.3.1
5.3.2
5.3.3
5.3.4
5.3.5
5.3.6
5.3.6.1
5.3.6.2
5.3.7
5.3.7.1
5.3.7.2
5.3.8

293
294
294
295
296
298
299

Slurry catalytic reactors
Introduction
Processes carried out in slurry catalytic reactors

Process design issues
Interphase mass transfer and kinetics
Mechanically agitated tanks and three-phase sparged reactors
Design of bubble slurry column reactors (BSCR)
Hydrodynamic characteristics of BSCR
Design models for slurry bubble reactors
Scale-up of slurry catalytic reactors
Scale-up of mechanically stirred reactors (MSSR)
Scale-up of BSCR
Examples

303
303
303
306
307
310
319
319
327
328
328
330
331

References

335

5.4

5.4.1
5.4.2
5.4.2.1
5.4.2.2
5.4.2.3
5.4.3

337
337
342
342
345
346
348

Catalytic reactors for olefin polymerizations
History, catalysts, polymers and process elements
Fundamentals of modelling
Modelling of polymerization kinetics
Modelling of the molecular weight distribution
Single particle modelling
The SPHERIPOL process

350

References
o

6.1
6.1.1

6.1.2
6.1.3
6.1.3.1
6.1.3.2
6.1.3.3

Separation operations and equipment

351

Pressure distillation

352
352
353
354
354
358
360

Introduction
Examples of pressure distillation
Interphase mass transfer and two-film theory
Two-film theory for distillation and dilute systems
Two-film theory for concentrate systems
Additivity of resistances

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xiv

6.1.4
6.1.4.1
6.1.4.2
6.1.4.3
6.1.4.4
6.1.5

Transfer Unit concept
HTU=Height equivalent to one transfer unit
HETP=Height equivalent to one theoretical plate
NTU=Number of transfer units
Efficiency
Effects of the total pressure

361
361
362
362
365
367

6.2
6.2.1

Packed towers: random and structured packings
Maximun column capacity

368

368

6.2.2

Efficiency

370

6.3
6.3.1

Tray columns
Flow regimes

371
371

6.3.2

Downcomer flooding and flooding

371

6.3.3
6.3.4
6.3.5
6.3.6

Liquid residence time
Liquid velocity

Downcomer backup
Tray efficiency

372
372
373
374

6.4

Trays or packings?

374

6.5

Conclusions for pressure distillation

375

References of sections 6.1, 6.2, 6.3, 6.4, 6.5

376

6.6
6.6.1
6.6.2
6.6.2.1
6.6.2.2
6.6.2.3

6.6.2.4
6.6.2.5
6.6.3
6.6.4

Extraction from solids
Fundamentals
Design criteria
Specific basic data
Thermodynamic conditions
Mass transfer
Process optimization by means of the T-S diagram
Separation of dissolved substances
Cascade operation and multi-step separation
Main applications

378
378
382
382
385
386
387
390
390
392

6.6.5

Specific application processes


393

References of section 6.6

394

6.7.1

Extraction from liquid mixtures
Introduction

396
396

6.7.2
6.7.2.1
6.7.2.2
6.7.2.3

Operation methods
Single-stage extraction
Multistage cross-flow extraction
Multistage countercurrent extraction

6.7.3

Modelling of countercurrent high pressure extraction

396

396
397
398
400

6.7

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XV

6.7.4
6.7.4.1
69
69
6.7.4.4
6.7.5

Types of extraction columns
Extraction columns without internals
Plate columns
Packed columns
Columns with energy input
Applications

References of section 6.7

400
400

400
401
402
402
402

Safety and control in high pressure plant design and operation

4O5

7.1

General safety aspects in high-pressure facilities

406

7.1 91

Safety aspects in design and operation

406

7.1 .2

Safety aspects due to changing properties with high pressure

408

7.1 .3
7.1 .4


Protective design and construction
Design criteria of buildings

411
414

Plant operation

418

Testing procedures and inspections

419

o

7.1 .5
7.1.6

References

420

7.2

Runaway of polyethylene reactors

7.2.1


General remarks

421
421

7.2.2

Decomposition reaction

421

7.2.3
7.2.3 9
7.2.3.2
7.2 9
7.2.3.4
7.2.4
7.2.5
7.2.5 9
7.2.5.2

Critical conditions
Homopolymerization
Influence of co-monomers
Influence of oxygen
Influence of decomposition sensitizers
Increase of pressure and temperature during decomposition
Loss prevention
Relief devices
Venting systems


423
423
423
424
425
426
427
427
428

References

429

7.3

Safety in high-pressure extraction plants

430

7.3.1

Protection of individual pressure ranges

431

7.3.2

Use of safety valves and rupture discs


433

7.3.3

Interlocking systems

434

7.3.4

Safety analysis

434

7.3.5

Controls and computerized systems

435

References

435

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xvi


So

Economics of high pressure processes

437

8.1

High-pressure extraction plants

438

8.1.1
8.1.1.1
8.1.1.2
8.1.1.3

Description of standardized units
Laboratory units
Medium scale units
Large scale units

438
438
439
439

8.1.2

Feasibility studies


440

8.1.3

Influence of design

440

8.1.4

Influence of process parameters

445

8.1.5

Influence of financing

450

References

452

8.2

High-pressure polymerization of ethylene

8.2.1

8.2.2
8.2.3
8.2.4

Consumption of polyethylene in Western Europe
General remarks
Capital costs
Production costs and total costs

453
453
454
454
455

8.2.5

Sensitivity analysis

457

8.2.6

Comparison of economics of high- and low-pressure process

458

References

459


8.3
8.3.1

Precipitation by Supercritical Anti-solvent
Rationale

460
460

8.3.2
8.3.3
8.3.4

Process description
Process simulation
Capital cost evaluation

8.3.5
8.3.6

Manufacturing cost evaluation
Cash-flow analysis

460
461
465
465

8.3.7


Conclusions

469
470

References

471

Applications

473

Chemical reactions in Supercritical Solvents (SCFs)
Introduction

474

9.1 .1
9.1 .2

SCFs as reactants

474

9.1 .3

SCFs as catalysts


475

9.1 .4

SCFs as solvents

476

9.1 .5

SCFs as a tool for product separation

477

9.1 .6

Reactions involving gases

479

.

9.1

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474


XVll


9.1.7
9.1.8

Continuous organic reactions
Future developments

481
482

References

483

9.2

Enzymatic reactions

486

9.2.1
9.2.2
9.2.2.1
9.2.2.2
9.2.2.3
9.2.2.4
9.2.2.5
9.2.2.6

Introduction

Enzymes
Enzyme stability in supercritical fluids
Effect of water activity
Effect of pressure
Effect of temperature
Number of pressurization-depressurization steps
Inhibition of enzymes

486
487
487
487
488
488
488
489

9.2.3
9.2.3.1
9.2.3.2
9.2.4

Enzyme reactors
Process schemes and downstream processing schemes
Processing costs
Conclusions

490
490
492

493
494

References
9.3
9.3.1
9.3.2
9.3.2.1
9.3.2.2
9.3.2.3
9.3.3
9.3.3.1
9.3.3.2
9.3.3.3
9.3.3.4
9.3.3.5

Hydrogenation under supercritical single-phase conditions
Introduction
Traditional hydrogenation processes
Gas-phase hydrogenation
Gas-liquid hydrogenation
Important process parameters
The supercritical single-phase hydrogenation
Single-phase conditions
Measurement of phase behavior in complex reaction mixtures
Connecting the different reaction systems
Impact of using supercritical single-phase hydrogenation technology
Outlook


References

496
496
497
497
498
499
502
502
504
504
505
506
506

9.4

Supercritical Water Oxidation (SCWO). Application to industrial
wastewater treatment

9.4.1

Introduction

9.4.2
9.4.2.1
9.4.2.2
9.4.2.3
9.4.3

9.4.3.1
9.4.3.2

Supercritical water as a reaction media
Physical properties of supercritical water
Oxidation reactions in SCWO
Catalysis
SCWO process description
Feed preparation and pressurization
Reaction

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509
509
510
510
511
511
511
511
512


XVlll

9.4.3.3 Cooling and heat recovery
9.4.4
Design considerations
9.4.4.1 Reactor configuration

9.4.4.2 Materials of construction
9.4.4.3 Solids separation
9.4.4.4 Heat exchangers
9.4.5
Other oxidation processes of wastewater at high pressure
9.4.5.1 Wet-air oxidation
9.4.5.2 Deep-shaft wet-air oxidation
9.4.6
SCWO applications to wastewater treatment
9.4.6.1 Pilot-plant operations
9.4.6.2 Example of operation with an industrial waste: cutting oil waste
9.4.6.3 Commercial process
9.4.6.4 Economic features

513
513
513
515
518
519
520
520
520
522
522
523
523
523

References


524

9.5

High pressure polymerisation with metallocene catalysts

9.5.1

Advantages of high-pressure polymerization with metallocenes

527
527

9.5.2
9.5.3

Catalyst and co-catalyst
Reaction mechanism and kinetics

528
530

9.5.4

Productivity

532

9.5.5


Properties of metallocene-based polyethylene

533

9.5.6
9.5.7

Technology of the process
Further developments

534
535

References

536

9.6

Supercritical Fluid Extraction and Fractionation from Solid Materials
Decaffeination of coffee and tea and extraction of hops
Decaffeination of green coffee beans
Decaffeination of tea
Preparation of hop extracts with CO2

537

9.6.1
9.6.1.1

9.6.1.2
9.6.1.3
9.6.2
9.6.2.1
9.6.2.2
9.6.2.3
9.6.2.4
9.6.2.5
9.6.2.6

Extraction of spices and herbs
Description of a spice plant
Extraction of essential oils
Extraction of pungent constituents
Production of natural colorants
Production of natural antioxidants
Production of high-value fatty oils

543
546
547
553
554
561
563

Depestisation of vegetal raw materials
9.6.3
9.6.3.1 Decontamination of the rice
9.6.3.2 Depestisation of Ginseng


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537
537
540
541

565
566
569


xix
References

571

9.7
9.7.1
9.7.1.1
9.7.1.2
9.7.1.3
9.7.1.4

576
576
576
577
578

579
580
580
580
581
582
582
582
583
583
583
583

9.7.2
9.7.3
9.7.3.1
9.7.3.2
9.7.3.3
9.7.3.4
9.7.3.5
9.7.4
9.7.4.1
9.7.4.2
9.7.4.3

High pressure polymer processing
Introduction
State of the art in polymer thermodynamics
Special polymer systems
Modelling polymer systems

Experimental methods in modelling polymer systems
Phase behaviour of polymer blends under pressure
High-pressure applications
Process optimization
Enhanced processing of polymer blends
Polymer particles
Plastics recycling
Reactive polymer blending
Future challenges
Controlled synthesis
Supramolecular structures
Morphology of polymer materials

584

References
9.8
9.8.1
9.8.2
9.8.3
9.8.3.1
9.8.3.2
9.8.3.3
9.8.4
9.8.4.1
9.8.4.2
9.8.4.3
9.8.5
9.8.5.1
9.8.5.2

9.8.5.3
9.8.6
9.8.6.1
9.8.6.2
9.8.7
9.8.7.1
9.8.7.2
9.8.7.3

Precipitation of solids with dense gases
Introduction
State of the art of material processing using Supercritical Fluids
Crystallization from a Supercritical Solution (CSS)
Fundamentals
Design criteria
Applications
Rapid Expansion of Supercritical Solutions (RESS)
Fundamentals
Design criteria
Applications
Gas Antisolvent Processes (GASR, GASP, SAS, PCA, SEDS)
Fundamentals
Design criteria
Applications
Particles from Gas-Saturated Solutions (PGSS)
Fundamentals
Design criteria
Application of PGSS process for micronisation
Glycerides
Cocoa butter

Pharmaceuticals

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587
587
587
587
587
588
589
589
589
589
590
592
592
593
593
596
596
598
599
600
603
604


XX


9.8.7.4
9.8.7.5
9.8.7.6
9.8.8

PGSS ofpolyethyleneglycols
Economy of the process
The advantages of PGSS
Conclusions

606
608
608
609

References

609

9.9
9.9.1
9.9.2
9.9.2.1
9.9.2.2
9.9.3
9.9.4
9.9.4.1
9.9.4.2
9.9.4.3
9.9.5


612
612
613
613
613
614
615
617
618
620
622

Pharmaceutical processing with supercritical fluids
Introduction
Separation processes
Fractionation/purification by precipitation
Supercritical Fluid Chromatography
Extraction and purification (SFE)
Particle formation
Rapid Expansion
Recrystallization by Supercritical Anti-solvent
Impregnation with Supercritical Fluids
Future developments

References

623

9.10

9.10.1
9.10.2
9.10.2.1
9.10.2.2
9.10.3
9.10.3.1
9.10.3.2
9.10.4

626
626
626
626
628
632
632
634
638

Treating microorganisms with high pressure
Introduction
Hydrostatic high pressure
State of the art
Equipment and methods
Supercritical CO2 treatment
State ofthe art
Equipment and methods
Conclusions

References


638

9.11
9.11.1
9.11.2
9.11.2.1
9.11.2.2

Dry cleaning with liquid carbon dioxide
Introduction
Dry-cleaning processes
Conventional dry cleaning
Dry cleaning with liquid carbon dioxide

9.11.3
9.11.3.1
9.11.3.2
9.11.3.3
9.11.4

The CO2 dry-cleaning process
Fundamentals
Garments agitation
Machine configurations
Conclusions

641
641
642

642
642
643
643
645
647
648

References

648

Subject Index

651

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xxi

LIST OF CONTRIBUTORS

Alberto Bertueco

Dipartimento di Principi e Impianti di Ingegneria Chimica (DIPIC) Universit/l di Padova
Via Marzolo, 91-35131 Padova Italy
Maria Jos~ Cocero

Departamento de Ingenieria Quimica, Universidad de Valladolid

Prado de la Madalena SP-47005 Valladolid, Spain
Nieola Elvassore

Dipartimento di Principi e Impianti di Ingegneria Chimica (DIPIC) Universit/t di Padova
Via Marzolo, 9 1-35131 Padova Italy
Theo W. De Loos

Faculty of Applied Science, Department of Chemical Technology
Laboratory of Applied Thermodynamics and Phase Equilibria
Delft University of Technology
Julianalaan 136 NL-2628 BL Delft, The Netherlands
Thomas Gamse

Institut fur Thermische Verfahrenstechnik und Umwelttechnik Erzherzog Johann Universit~it
Infeldgasse, 25 A-8010 Graz, Austria
Sander van den Hark

Department of Food Science, Chalmers University of Technology
P.O. Box 5401 SE-40229 Grteborg, Sweden
Magnus Hiirriid

Department of Food Science, Chalmers University of Technology
P.O. Box 5401 SE-40229 Grteborg, Sweden
Z;eljko Knez

Department of Chemical Engineering University of Maribor
P.O. Box 222, Smetanova 17, SI-2000 Maribor, Slovenia
Ireneo Kikic

Dipartimento di Ingegneria Chimica, dell'Ambiente e delle Materie Prime

Universitfi degli Studi di Trieste
Piazzale Europa, 1 1-34127Trieste, Italy

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XXll

Ludo Kleintjens

DSM Research and Patents
Postbus 18, NL6160 MD Geleen, The Netherlands
Eduard Lack

NATEX GmbH Prozesstechnologie
Hauptstrasse, 2 A-2630 Ternitz, Austria
Andr~ Laurent

Ecole Nationale Sup~rieure des Industries Chimiques (ENSIC)
B. P. No. 451, 1. Rue Granville F-54001 Nancy Cedex, France
Gerhard Luft

Department of Chemistry, Darmstadt University of Technology
Petersenstr. 20, D-64287 Darmstadt, Germany
Siegfried Maier

Formerly Research and Development, BASF AG,
D 67056 Ludwigshafen, Germany
Maj-Britt Macher


Department of Food Science, Chalmers University of Technology
P.O. Box 5401 SE-40229 G6teborg, Sweden
Rolf Marr

Institut fur Thermische Verfahrenstechnik und Umwelttechnik Erzherzog Johann UniversiRit
Infeldgasse, 25 A-8010 Graz, Austria
Nicola Meehan

School of Chemistry, University of Nottingham
University Park, Nottingham NG7 2RD England
Poul Moiler

Augustenborggade 21B, DK-8000 Aarhus C, Denmark
Paolo Pallado

via M. Ravel, 8 35132 Padova Italy
Martyn Poliakoff

School of Chemistry, University of Nottingham
University Park, Nottingham NG7 2RD England
Francisco Recasens

Universitat Polit~cnica de Catalunya
Departamento de Ingenieria Quimica
E.T.S.I.I.B. Diagonal, 647 E-08028 Barcelona, Spain

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xxiii

l-lelmut Seidlitz

NATEX GmbH Prozesstechnologie
Hauptstrasse, 2 A-2630 Ternitz, Austria
Bela Sim~indi

Budapest University of Technology and Economics, Department of Chemical Engineering
Budapest, XI., Mtiegyetem rkp. 3. K. 6p.mfsz. 56. H-1521, Budapest, Hungary
Sara Spilimbergo

Dipartimento di Principi e Impianti di Ingegneria Chimica (DIPIC) Universit~ di Padova
Via Marzolo, 9 1-35131 Padova Italy
Alberto Striolo

Dipartimento di Principi e Impianti di Ingegneria Chimica (DIPIC) Universit& di Padova
Via Marzolo, 9 1-35131 Padova Italy
Fakher Trabelsi

Universitat Polit6cnica de Catalunya
Departamento de Ingenieria Quimica
E.T.S.I.I.B. Diagonal, 647 E-08028 Barcelona, Spain
Enrique Velo

Universitat Polit6cnica de Catalunya
Departamento de Ingenieria Quimica
E.T.S.I.I.B. Diagonal, 647 E-08028 Barcelona, Spain
Gerhard Vetter

Department of Process Machinery and Equipment,
University of Erlangen-Nuremberg, Cauerstr. 4, D 91054 Erlangen, Germany

Guenter Weickert

P.O. Box 217 NL-7500 AE Enschede, The Netherlands
Eekhard Weidner

Lehrstuhl fiir Verfahrenstechnische Transportprozesse, University Bochum
Universit~itsstr. 150, 44780 Bochum, Germany
Federieo Zanette

Dipartimento di Principi e Impianti di Ingegneria Chimica (DIPIC) Universit~ di Padova
Via Marzolo, 9 1-35131 Padova Italy

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xxiv

ABOUT THE EDITORS

Alberto Bertucco (age 46), Professor of Chemical Engineering at the University of Padova,

Italy: Chairman of the Working Party High Pressure Technology of the European Federation
of Chemical Engineers, with long-term research activity in the field of Supercritical Fluids
Applications.
Gerhard Vetter (age 68), Professor of Chemical Engineering at the University of ErlangenNuremberg, Germany: many years of experience in High Pressure Plant Equipment and
Process Machinery for Fluids and Bulk Solids.

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