Process Intensification in Fine Chemicals and

Transcription

Process Intensification
in Fine Chemicals and
Advanced Materials:
methodology and achievements
Process Intensification in Fine Chemicals and Advanced Materials
ENKI Innovation www.enki2.com
Jan 2007
1.Innovation, an answer to the
challenges of Sustainable Development
2. Process Intensification, a new paradigm in Chemical
Engineering
3. Process Intensification strategies
4. Process Intensification for Fine Chemicals and
Advanced Materials: EXAMPLES and novelties
5. Perspective: Intensified Product Engineering
Jan 2007
The chemical industry identifies innovation and
sustainable development as a chance.
People
Planet
Profit
The challenge for the process industries is not only to provide
products and services to our consumer society, but to
perform it with markedly lower reliance on raw
materials, energy, labor and waste.
Jan 2007
The chemical industry identifies innovation and
sustainable development as a chance.
Through the application of ‘green’ chemistry and engineering, the
industry has already implemented innovations in the field
of renewable resources, eco-efficient products, energy efficiency,
waste reduction and reuse, inherently safer processes:
‘ Products and processes for a sustainable chemical industry’
industry
Green Chem 2004 (6), 544-556
a tutorial paper from CEFIC with 158 references
…but
Jan 2007
The chemical industry identifies innovation...
but
R&D intensity drops
Jan 2007
The chemical industry identifies sustainable development…
but has a serious
Courtesy A.Stankiewicz
credibility problem…
Jan 2007
Many claim to be sustainable…
BUT very few prove it !
Î we need quantitative, robust, shared
metrics.
A communication disaster: the fight against REACH
Î we need ethical managers, not ‘sharks’.
Many talk of green engineering
(innovation ‘blah-blah’, reinvention of the wheel)
few apply basic principles.
ex: Î we need exergy analysis (environmental thermodynamics))
Jan 2007
1. Innovation, an answer to the challenges of
Sustainable Development
2. Process Intensification, a new
paradigm in Chemical Engineering
Jan 2007
Courtesy A.Stanjiewicz
De Re Metallica
G.Agricola, 1556
Did we progress
in 450 years?
Jan 2007
Early pharmaceutical chemistry
did we progress in 2000 years ?
Jan 2007
Yes, we progressed since 1556... we built large ‘cathedrals’.
cost ≈ size0.66
Why then should we miniaturize our production tools ?
Jan 2007
Dr. Deibel
Pdt Corporate
Engineering
at BASF
in CHE Manager
(2006)
The classical world-scale plant is phased-out:
• Paradigm change in plant engineering
• Time-to-market
• Modular plant techniques needed
• Microprocess engineering will have a role
on plant philosophy more than on absolute size
Same view: Dr. Aldo Belloni (Linde board of directors)
in Process 13, 4 (2006) 64
Jan 2007
PI historical perspective:
late 1970s: Ramshaw developped Higee at ICI
reduce the plant size/cost
Courtesy DSM
Is our future a flexible mini-plant built on a table or
bolted on a wall, from modular elements ?
Jan 2007
PI, a new strategy:
Instead of adapting the physico-chemical
transformation to existing, known, depreciated
but often inadapted equipment…
Process Intensification is a design strategy
to adapt the process to the chemical reaction
“ Doing more with less ”
DSM
Urea Plus
@ adapting the size of equipment to the reaction
@ replacing large, expensive, inefficient equipment by
smaller, more efficient and cheaper
@ choosing the technology best suiting each step
@ sometimes combining multiple operations in fewer
apparatuses.
Jan 2007
Unit operations: A.D.Little 1907
Transport phenomena: 1960 Bird, Steward, Lightfoot
Process Intensification, serving SD goals
EFCE
WP PI
Jan 2007
« Reengineering the Chemical Processing Plant »
R.Bakker, Marcel Dekker ed. 2003
Reach intrinsic kinetics of phenomena
maximize transfer rate
Fick law: flux = coefficient x interface x gradient
Jan 2007
Equipment already exist that can
be characterized by their E & m
transfer performances
Courtesy BRITEST
Rotating
Packed Bed
Mass Transfer
Static Mixer
Pulsed
Column
Microreactor
Static Mixer/
Plate Exchanger
Spinning Disc
Reactor
Educter
Loop
Reactor
Jacketed
Stirred Tank
Plate
Exchanger
Heat Transfer
Jan 2007
1. Innovation, an answer to the challenges of Sustainable
Development
Engineering
3.Process Intensification strategies
in Fine Chemicals, Spec Chemicals,
Pharmaceuticals, Advanced Materials
Jan 2007
Process Intensification strategy
Tactics 1: multifunctionality (design methodology)
unit operations have to be ‘compatibilized’
Tactics 2: thermodynamics
increase potential of reactants, by activity or diffusivity
miniaturization to increase force fields
Tactics 4: energetics
Tactics 3:
create force fields at a mesoscopic level
Jan 2007
1- Multifunctionality in PI
for Fine & Spec Chemicals and Advanced Materials
X reactive distillation:
@ convincing demos in petrochemicals...
@ ...narrow operating windows, mediocre flexibility
X hybrid separations:
@ membrane-reaction coupling: some applications
@ in fine chem, bio... where mild media, low requirements
@ membranes still show low performances
X static mixers are commonplace, including reactive versions,
but their performances are average
X monolithic reactors (supporting catalysts, enzymes, cells)
@ increasingly used in loop reactors
@ many external loops (« intensive » engineering)
X chromatographic reactors, SMB are industrial
Jan 2007
Loop reactors:
Air Products retrofit of
hydrogenators with a monolithic
reactor: productivity x 10 to 50.
Jan 2007
Chromatographic reactors, Simulated Moving Beds:
example of DSM 7-ADCA in Delft (NL)
Jan 2007
2- Thermodynamics (solvents) in PI
X neoteric solvents:
super-critical fluids (SCF) and ionic liquids (IL)
@ still a curiosity, despite recent announcements (and to
the exception of SCF extractions):
applications are very specific
SCF are not good solvents
costs are not convincing
IL toxicity is not assessed !
@ some investment in IL engineering by major companies
X trend = solvent-free processes
REM : Water is not a “green” solvent ! but bio-based oxygenates are.
Jan 2007
Ionic liquids (IL) organic salts with low melting point (usually <100°C)
- vapor pressure is extremely low, no solvent lost
- large range of temperature (200 to 300 Kelvins)
Is this all new ?? a fashion-driven rediscovery of early work
in the 1970s on ‘molten organic salts’…
Example of the BASF
BASIL solvent-free process
OEt
P
OEt
Cl
P
N
+
Cl
2 EtOH
+
DEOPP
2
N
N
Biphasic Acid Scavenging utilizing Ionic Liquids
N+
H
Cl -
Jan 2007
SC media: DuPont 275 M$ for a tetrafluoroethylene SC polymerization
production unit. Fluorinated vinyl polymers are non-explosive when
mixed with CO2 and can be continuously polymerized in SC medium.
Thomas Swan C° world’s first multireaction super-critical flow reactor, a
commercial-scale continuous facility for
running reactions in SC CO2
1000 tpa
M.Poliakoff (U.Nottingham)
CO2-expanded solvents:
Continuous hydrogenation of sertraline
in scCO2/THF: commercial route to
Zoloft® (Pfizer)
Jan 2007
X trend = solvent-free processes, mecano-chemistry
LIST
reactive extrusion, optionally under SC conditions
Jan 2007
3- Miniaturization in PI
X microreactors start booming
@ microchannels, microfilms, microcolumns
@ mono-, di- or tri-phasic media
@ drivers:
9 switch from batch to continuous
9 new operating conditions
9 control of properties of final product/formula
9 respect of regulations, incl. FDA.
X World-class manufacturers and engineering:
IMM, Siemens, Hitachi, Velocys, BTS,... ,...
X MESO-technologies: structured at the millimetric scale
Jan 2007
e
th
in s
t
si vice
i
v e
k
c ro d
i
qu ic
a fm
o
”
o
o
“z
Jan 2007
Degussa + Uhde, Demis Projekt:
microstructured epoxidation reactor
Jan 2007
Miniaturization in PI for Fine Chemicals and Advanced Materials
X MESO-technologies: structured at the millimetric scale,
best compromise performance/operability,
now widely developed
AlfaLaval
X Compact reactive
heat exchangers
(Marbond, Heatric,
Alfa-Laval)
Jan 2007
4- Alternative energy in PI
X still very few industrial applications of microwaves, acoustic
fields, electric fields, plasmas, etc...
X in the other hand, gravitational fields find industrial
applications:
Spinning Disks, Rotating Packed Beds and Tube Reactors
are still under development
Not yet widely adopted, the challenge of size reduction
favors them.
X at the R&D level (excl. rare cases): impinging jet reactors,
supersonic, oscillating reactors, intensive rotor-stator, ...
Jan 2007
Energy sources such as UV light, microwaves, ultrasounds are
used in a controlled way to heavily increase the efficiency of a
chemical reaction, thus making it more eco-friendly…
…but little is known on commercial applications
Challenge = design rules
plasma reactor
microwave generators
electrosynthesis
Jan 2007
Solar energy: a curiosity...
C. Schiel et al, 2001
PROPHIS solar
photoreactor
Jan 2007
Gravitational fields
industrial applications from petrochemicals to ingredients:
Dow Chemicals
Protensive Higee
Shengli Oil
Stripping of
solvents
ultra-fast
cooking
(2 s @ 130°C)
Jan 2007
Small energy input, large effects:
Baffle geometry coupled with intensity of oscillation produced
by pistons control mixing
NiTech
Cambridge Reactor Design
Jan 2007
Development
2. Process Intensification, a new paradigm in ChEng
4.Process Intensification for Fine Chemicals
Jan 2007
PI to reduce the plant size:
why is ‘smaller beautiful’ ?
Jan 2007
In Fine Chemicals and Advanced Materials:
‘smaller is beautiful’ because
smaller is safer !
UCC, Bhopal 3 Dec 1984:
cloud of 41 tons MIC
>2 500 killed
1 ppm COCl2
An inventory of 10 kg MIC
would have been sufficient
(D.Hendershot, CEP 2000)
Jan 2007
Accidents are due to large inventories !
Courtesy TU Delft
Jan 2007
continuous mode performs better
ref: Merck
5 MINI-reactors
0°C < 1 mn
Batch 5m3
-20°C 5h Yield 72%
continuous
yield >92%
Many cryo batch processes are now replaced by
meso-techs for continuous (quasi) room T processes
Jan 2007
smaller is more flexible
good for on-site on-demand production
ref: A.Green BHRG
Delocalized productions, close to customer, with much lower
inventories…
but also delocalized risk !
- Interox: 1 ton/day peroxysulfuric acid (1s in a 20 cm3 tubular reactor)
- Kvaerner: phosgene COCl2 modular generator, point-of-use, skid-mounted
- hydrogen cyanide, chlorine dioxide, ethylene oxide, …
Jan 2007
‘dream reactions’ are now possible
High T and P processing:
T not limited by solvent boiling point
Î operation in liquid phase at elevated
pressure (100 bar is easy)
ref: IMM
Use of dangerous reagents:
ex: fluorination by F2 takes a few milliseconds in a miniature falling film
Explosive regimes:
ex: even in detonating mode, ie. with
mixtures of pure hydrogen and oxygen
Jan 2007
Selected examples of Process Intensification
for Fine Chemicals
ex 1-4 Microprocessing chemical pilot plants
(FZK-DSM, MCPT-Idemitsu, IMM-X’ian Chem, CPC)
ex 5- SiProcess (Siemens)
ex 6- RAPTOR (AET Group)
ex 7- Spinning Tube-in-tube (Kreido)
for Advanced Materials
ex 8- Micromembrane emulsifier (Velocys)
ex 9- Micromixer emulsifier (IMM)
Jan 2007
Process Intensification for Fine Chemicals: example 1
fine chemicals plant in a ‘shoe-box’ FZK + DSM
Forschungszentrum Karlsruhe (www.fzk.de):
65 cm, 290 kg, throughput 1700 kg of liquid chemicals per hour. “Micro”
in its interior: micromixers and several ten thousands of microchannels.
Reaction heat of several 100 kW is removed.
Jan 2007
Chemical production with FZK microstructured reactor at
DSM Fine Chemicals in Linz, Austria
• Within 10 weeks:
300 tons of high-value product.
FZK
• Product yield increased compared
to conventional processing
• Less raw material use and less waste
generation, more process safety
• Now permanently in operation
(announced at Achema May 2006)
Other announcements:
Clariant (2005): 1000 tpa pigment plant (?)
Degussa (2006): several production plants (?)
Jan 2007
radical polymerization
Idemitsu Kosan+Kyoto U
ID = 500µm
94 pieces
inlet
L=60 cm
outlet
cooling shell )
heating shell
www.mcpt.jp
“Pilot plant” at Kyoto U
Dr. T.Iwasaki
Plant running at industrial
site of Idemitsu Kosan ?
10 t/a
3.5m × 0.9m
Jan 2007
nitroglycerin pilot-plant Xian Chemicals + IMM
HO
OH
OH
HNO3 / H2SO4
O 2N
O
O 2N
O
NO2
O
C&EN cover story 30May05
IMM developed in Mainz
Xian invested ~5 M €
•
•
•
•
•
Nitroglycerin production on a pilot plant level (15 kg/h NG, >100 l/h)
NG used as medicine for acute cardiac infarction
Product quality on highest grade
Plant to operate safely and fully automated
Environment protection by advanced waste water treatment & closed cycle
Jan 2007
Pharmaceutical chemistry, CPC
Synthacon on a contract basis:
• a commercial multiproduct plant near Leipzig,
by mid-2006, producing ~20 tpa
• high added value chemicals (niche
applications) with a range from 1 kg to 100 kg
for pharmaceuticals
Sigma-Aldrich installed a standard Cytos in
Buchs. Many catalog products are produced
under lab conditions in flasks of up to 20 L.
Of the 2000 compounds in this portfolio, about
800 could be produced in microreactors
with little or no process modification.
Jan 2007
chemical microprocessor
SIEMENS
SIPROCESS
www.siemens.com/siprocess
Jan 2007
chemical microprocessor
SIEMENS
Combination of modularity with
integrated
automation.
Each
module has its own electronics
and sensors to control the internal
module functions.
The electronics are connected to
the
higher-level
automation
system based on SIMATIC PCS 7
via a bus system, to which they
are linked by plugging the module
into a rack.
www.siemens.com/siprocess
Jan 2007
RAPTOR continuous hydrogenator
AET Group
Injection gas, reagents
inlet
Jacket heating
and cooling
www.aetgroup.com
Réacteur Agité
Polyvalent à Transfert
Optimisé Rectiligne
Motor
Reaction chamber
outlet
Operating pressure:
Operating temperature:
Heat exchange:
250 bar
-100 to +300°C
> 150 m²/m3
(vs. batch reactor: <5 m²/m3)
Stirrer rotating speed:
Feed flowrate:
Material:
Length:
0 to 1500 rpm
0 - 150 l/h
Hastelloy
2m
Jan 2007
RAPTOR 1: diameter 8mm, 200 bar, 200°C
Production tpa
1400
1200
1000
800
600
400
200
Residence time (s)
0
0
20
40
60
80
100
Jan 2007
C00001-01 Copyright AETGROUP SAS 2005
Spinning Tube in Tube reactor
Kreido Labs
Couette Flow in a narrow annular gap
between a stationary stator and a
rapidly rotating, concentric, internal
rotor, producing a coherent thin film in
a high shear field
STT
triglyceride + 3 MeOH Æ glycerol + 3 fatty acid methyl ester
mass transfer limited !
biodiesel at a residence time of 0.5 second
complete pipe-to-pipe biodiesel production unit (STT 30G)
Jan 2007
Development
Engineering
4. Process Intensification for Fine Chemicals and Advanced
Materials
5. Perspective:
Intensified Product Engineering
Jan 2007
Opportunities for microprocessing
and process intensification
Î Intensified product engineering:
“precision engineering”

sharpening property distribution
MW, particle diameter, size, etc.

challenge: high Peclet #
(lowest possible axial dispersion)

potential for liquids and solids
Jan 2007
io
n
In
liq te
u i ns i
ds f i
e
AN d
D for
so mu
lid la
s t
Jan 2007
Mono-disperse silica nanoparticles
(segmented flow microreactor)
Jan 2007
Process Intensification for Advanced Materials: example 8
micro-membrane emulsifier
Velocys
Transmembrane pressure drop: one phase is dispersed thru pores
(principle known since early 1990s).
Fine droplets directly generated by build-up and detachment at the
surface of the membrane.
Jan 2007
• High shear at wall,
lower shear in bulk
• Small droplet sizes,
uniform distribution
• Rapid, in-line heating &
cooling
• Overcome scale-up
challenges
• Small, compact units
0.2-5 mm
not micro:
milli !
Jan 2007
www.velocys.com
Jan 2007
Process Intensification for Advanced Materials: example 9
micro-mixers emulsifier (Institute Mikrotechnik Mainz)
Jan 2007
Jan 2007
CONCLUDING REMARKS
• to implement PI, a reasonable set of basic data (kinetics,
transfer rates) is necessary
• in miniaturization, the micron level is unnecessary : a
millimeter scale is often sufficient and corresponds to an
optimal ratio performance-to-operability
• the flexibility and the versatility of tools are still a challenge,
as well as the process control (Engg methodologies required !)
• in the context of sustainable development, technologies able
to confine reagents in a fully controlled process is a major
strategic advantage
• companies in developing countries have identified PI as a
catch-up issue
• strong differentiation on products can be obtained by process
intensification of formulation (emulsions, suspensions,
micro/nano particles)
• A good example of the ‘rush-to-be-second’ syndrom ???
Jan 2007

Process Intensification in Fine Chemicals and

Transcription

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