process intensification in fine chemicals and advanced ... · process intensification in fine...

Process Intensification in Fine Chemicals and Advanced MaterialsProcess Intensification in Fine Chemicals and Advanced Materials ENKI Innovation www.enki2.com Jan 2007ENKI Innovation www.enki2.com Jan 2007

Process IntensificationProcess Intensificationin Fine Chemicals and in Fine Chemicals and Advanced Materials:Advanced Materials:

methodology and achievementsmethodology and achievements


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


People

Planet Profit

The chemical industry identifies innovation and sustainable development as a chance.

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.


The chemical industry identifies innovation and sustainable development as a chance.

‘ Products and processes for a sustainable chemical industryProducts and processes for a sustainable chemical industry’

Green Green ChemChem 2004 (6), 5442004 (6), 544--556556

a tutorial paper from CEFIC with 158 referencesa tutorial paper from CEFIC with 158 references

…but

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:


The chemical industry identifies innovation...

but R&D intensity drops


Courtesy A.Stankiewicz

but has a serious credibility problem…

The chemical industry identifies sustainable development…


Many talk of green engineering(innovation ‘blah-blah’, reinvention of the wheel)

few apply basic principles.

ex: we need exergy analysis (environmental thermodynamics)))

Many claim to be sustainable…BUT very few prove it !

we need quantitative, robust, shared metrics.

A communication disaster: the fight against REACHwe need ethical managers, not ‘sharks’.


1. Innovation, an answer to the challenges of Sustainable Development






De Re MetallicaG.Agricola, 1556

Did we progress in 450 years?

Courtesy A.Stanjiewicz


Early pharmaceutical chemistrydid we progress in 2000 years ?


Yes, we progressed since 1556... we built large ‘cathedrals’.

Why then should we miniaturize our production tools ?

0.66sizecost ≈


Dr. DeibelPdt Corporate

Engineeringat 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


Courtesy DSM

reduce the plant size/cost

PI historical perspective:

late 1970s: Ramshaw developped Higee at ICI

Is our future a flexible mini-plant built on a table or bolted on a wall, from modular elements ?


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 ”adapting the size of equipment to the reaction replacing large, expensive, inefficient equipment by

smaller, more efficient and cheaperchoosing the technology best suiting each stepsometimes combining multiple operations in fewer

apparatuses.

DSM Urea Plus


Unit operations: A.D.Little 1907Transport phenomena: 1960 Bird, Steward, Lightfoot

Process Intensification, serving SD goals

EFCEWP PI


«« Reengineering the Chemical Processing PlantReengineering 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


Mass

Tra

nsf

er

Mass

Tra

nsf

er

Heat TransferHeat Transfer

Courtesy BRITEST

JacketedStirred Tank

Microreactor

Pulsed Column

LoopReactor

Rotating Packed Bed

Educter

Static Mixer

Static Mixer/Plate Exchanger

PlateExchanger

Spinning DiscReactor

Equipment already exist that can be characterized by their E & m

transfer performances




3.Process Intensification strategiesin Fine Chemicals, Spec Chemicals, Pharmaceuticals, Advanced Materials




Process Intensification strategy

Tactics 1: multifunctionality (design methodology) unit operations have to be ‘compatibilized’

Tactics 2: thermodynamicsincrease potential of reactants, by activity or diffusivity

Tactics 3: miniaturization to increase force fields

Tactics 4: energeticscreate force fields at a mesoscopic level


1- Multifunctionality in PIfor Fine & Spec Chemicals and Advanced Materials

reactive distillation:convincing demos in petrochemicals......narrow operating windows, mediocre flexibility

hybrid separations:membrane-reaction coupling: some applicationsin fine chem, bio... where mild media, low requirementsmembranes still show low performances

static mixers are commonplace, including reactive versions, but their performances are average

monolithic reactors (supporting catalysts, enzymes, cells) increasingly used in loop reactorsmany external loops (« intensive » engineering)

chromatographic reactors, SMB are industrial


Loop reactors: Air Products retrofit of hydrogenators with a monolithic reactor: productivity x 10 to 50.


Chromatographic reactors, Simulated Moving Beds:example of DSM 7-ADCA in Delft (NL)


2- Thermodynamics (solvents) in PIfor Fine & Spec Chemicals and Advanced Materials

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 specificSCF are not good solventscosts are not convincingIL toxicity is not assessed !

some investment in IL engineering by major companies

trend = solvent-free processes

REM : Water is not a “green” solvent ! but bio-based oxygenates are.


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’…

PCl

Cl N

N+ 2 EtOH + 2

POEt

OEt

N

NH+

Cl -

DEOPP

Biphasic Acid Scavenging utilizing Ionic Liquids

Example of the BASFBASIL solvent-free process


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 multi-reaction super-critical flow reactor, a commercial-scale continuous facility for running reactions in SC CO21000 tpa

M.Poliakoff (U.Nottingham)

CO2-expanded solvents:Continuous hydrogenation of sertralinein scCO2/THF: commercial route to Zoloft® (Pfizer)


trend = solvent-free processes, mecano-chemistry

reactive extrusion, optionally under SC conditions

LIST


3- Miniaturization in PIfor Fine & Spec Chemicals and Advanced Materials

microreactors start boomingmicrochannels, microfilms, microcolumnsmono-, di- or tri-phasic mediadrivers:

switch from batch to continuousnew operating conditionscontrol of properties of final product/formularespect of regulations, incl. FDA.

World-class manufacturers and engineering:IMM, Siemens, Hitachi, Velocys, BTS,... ,...

MESO-technologies: structured at the millimetric scale


a quick visi

t in th

e “zoo”

of micr

odevices


Degussa + Uhde, Demis Projekt:microstructured epoxidation reactor


Miniaturization in PI for Fine Chemicals and Advanced Materials

MESO-technologies: structured at the millimetric scale, best compromise performance/operability,now widely developed

AlfaLaval

Compact reactive heat exchangers (Marbond, Heatric, Alfa-Laval)


4- Alternative energy in PIfor Fine & Spec Chemicals and Advanced Materials

still very few industrial applications of microwaves, acoustic fields, electric fields, plasmas, etc...

in the other hand, gravitational fields find industrial applications:

Spinning Disks, Rotating Packed Beds and Tube Reactors are still under developmentNot yet widely adopted, the challenge of size reduction favors them.

at the R&D level (excl. rare cases): impinging jet reactors, supersonic, oscillating reactors, intensive rotor-stator, ...


Energy sources such as UV light, microwaves, ultrasounds are used in a controlled way to heavily increase the efficiency of achemical reaction, thus making it more eco-friendly…

…but little is known on commercial applicationsChallenge = design rules

plasma reactor microwave generators electrosynthesis


PROPHIS solar photoreactor

C. Schiel et al, 2001

Solar energy: a curiosity...


Shengli Oil

Dow Chemicals

Protensive Higee

Gravitational fieldsindustrial applications from petrochemicals to ingredients:

Stripping of solvents

ultra-fast cooking

(2 s @ 130°C)


Cambridge Reactor Design

Baffle geometry coupled with intensity of oscillation produced by pistons control mixing

Small energy input, large effects:

NiTech



2. Process Intensification, a new paradigm in ChEng


4.Process Intensification for Fine Chemicals



PI to reduce the plant size:why is ‘smaller beautiful’ ?


UCC, Bhopal 3 Dec 1984:cloud of 41 tons MIC

>2 500 killed

An inventory of 10 kg MICwould have been sufficient

(D.Hendershot, CEP 2000)

In Fine Chemicals and Advanced Materials:‘smaller is beautiful’ because

smaller is safer !

1 ppm COCl2


Courtesy TU Delft

Accidents are due to large inventories !


ref: Merck

Batch 5m3

-20°C 5h Yield 72%

5 MINI-reactors0°C < 1 mn

continuousyield >92%


continuous mode performs better

Many cryo batchcryo batch processes are now replaced by meso-techs for continuous (quasi) room T processes


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, …


smaller is more flexiblegood for on-site on-demand production

ref: A.Green BHRG



‘dream reactions’ are now possible

High T and P processing:T not limited by solvent boiling point

operation in liquid phase at elevated pressure (100 bar is easy)

Use of dangerous reagents:ex: fluorination by F2 takes a few milli-

seconds in a miniature falling film

Explosive regimes:ex: even in detonating mode, ie. with

mixtures of pure hydrogen and oxygen

ref: IMM


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 Materialsex 8- Micromembrane emulsifier (Velocys)

ex 9- Micromixer emulsifier (IMM)


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.

Process Intensification for Fine Chemicals: example 1fine chemicals plant in a ‘shoe-box’ FZK + DSM


Other announcements:Clariant (2005): 1000 tpa pigment plant (?)Degussa (2006): several production plants (?)

FZK

Chemical production with FZK microstructured reactor at

DSM Fine Chemicals in Linz, Austria

• Within 10 weeks:300 tons of high-value product.

• 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)


10 t/a 3.5m × 0.9m

“Pilot plant” at Kyoto UDr. T.Iwasaki

Plant running at industrial site of Idemitsu Kosan ?

heating shell

cooling shell )inlet

outletID = 500µm L=60 cm 94 pieces

Process Intensification for Fine Chemicals: example 2radical polymerization Idemitsu Kosan+Kyoto U

www.mcpt.jp


IMM developed in MainzXian 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

C&EN cover story 30May05

OHOH OH

OO O

O2N

O2N

NO2HNO3 / H2SO4

Process Intensification for Fine Chemicals: example 3nitroglycerin pilot-plant Xian Chemicals + IMM


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.

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

Process Intensification for Fine Chemicals: example 4Pharmaceutical chemistry, CPC


www.siemens.com/siprocess

Process Intensification for Fine Chemicals: example 5chemical microprocessor SIEMENS

SIPROCESS


www.siemens.com/siprocess

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.

Process Intensification for Fine Chemicals: example 5chemical microprocessor SIEMENS


Réacteur Agité Polyvalent à Transfert

Optimisé RectiligneReaction chamber

Injection gas, reagents

Motor

inlet

outlet

Jacket heatingand cooling

Operating pressure: 250 barOperating temperature: -100 to +300°CHeat exchange: > 150 m²/m3

(vs. batch reactor: <5 m²/m3)Stirrer rotating speed: 0 to 1500 rpmFeed flowrate: 0 - 150 l/hMaterial: HastelloyLength: 2 m

Process Intensification for Fine Chemicals: example 6RAPTOR continuous hydrogenator AET Group

www.aetgroup.com


C00001-01 Copyright AETGROUP SAS 2005

RAPTOR 1: diameter 8mm, 200 bar, 200°C

0

200

400

600

800

1000

1200

1400

0 20 40 60 80 100

Production tpa

Residence time (s)


Process Intensification for Fine Chemicals: example 7Spinning 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

triglyceride + 3 MeOH glycerol + 3 fatty acid methyl ester

mass transfer limited !

biodiesel at a residence time of 0.5 secondcomplete pipe-to-pipe biodiesel production unit (STT 30G)

STT





4. Process Intensification for Fine Chemicals and Advanced Materials



Opportunities for microprocessingand process intensification

Intensified product engineering:

“precision engineering”

sharpening property distributionMW, particle diameter, size, etc.

challenge: high Peclet #(lowest possible axial dispersion)

potential for liquids and solids


Inte

nsifi

ed fo

rmul

atio

n

liqui

ds A

ND s

olid

s


Mono-disperse silica nanoparticles(segmented flow microreactor)


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.

Process Intensification for Advanced Materials: example 8micro-membrane emulsifier Velocys


0.2-5 mm

not micro:milli !

• 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


www.velocys.com


Process Intensification for Advanced Materials: example 9micro-mixers emulsifier (Institute Mikrotechnik Mainz)


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 ???

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