IMM-microreactors

T H E C AT A L O G U E > chemical micro process technology made by imm

5/09

PREFACE

1 THE NEW CATALOGUE – DIVERSIFIED IN PAR PARTS TS & INTEGRA INTEGRATED TED AS APPROACH

It is always a pleasure to introduce the next generation of development and to sum up what this is about and what is beyond. The new catalogue comprises a diversified, but also refocused offer of microstructured reactors and their processing plants. All ears on benefit New technologies create new opportunities and may strengthen the competitiveness, but also demand for careful implementation and use at the right spot. Technological overshoot and veering away from demand is to be avoided. IMM’ IMM’s s micro process technology ever since is truly devoted to real-life applications in the field of chemical processing, fuel processing, consumer goods, etc. guided by a wealth of experience in customers’ needs. This ‘echo box’ mirrors the long lasting and steady information exchange about user’s practise from innumerable direct discussions, but also arising from the excerpts and essences attained from the global platforms such as symposia, platforms and expert groups’ meetings.

More than meets the eye Single developments into an entirely new direction should not be isolated, but should be governed and marshalled by a persistent general idea how to approach the endeavour. Leitmotifs of IMM’s process technology are:

• Scale-out – from from laboratory laboratory to production scale • System integration – from from single devices to integrated reactors and plants • Holistic view – from from conventional conventional to novel process windows • Accommodate as appropriate – from micro to milli scale

Continuing roots and shaping up for future quests

Central new feature in the ‘basket of goods’ are pilot- and production-scale microstructured reactors and whole respective reactor systems, stemming from validated and (partially) documented developments within industrial driven national and European projects; all oriented towards target production and prove (cost) competitiveness. Two such highlights exemplary for the whole approach & portfolio are a setup comprising a modular micro-reactor followed by a milli-scaled tube bundle for the production of ionic liquids at a capacity of 100 kg/d and pilot- and productionscale microstructured Falling Film Microreactors. Both have stood the test in demonstration processing at industrial sites. Both serve to show how micro process engineering can speed up the scale up process.

PREFACE

2 Branch and whole tree Process intensification is a dramatic and far-reaching change in chemical production technology. The same holds for microreaction technology as the major PI approach. Needed is interdisciplinary bridging in the format of a comprehensive and holistic micro process development. This may be subsumed in five PI pillars “Catalysts – Fabrication – Reactors – Plants – Processes”. It is the vision and skills on catalysts, fabrication and processes which adds to the hardware development based on reactors and plants.

Catalysts

Fabrication

Process Proces ses

Reactors Plants

IMM has developed brazing as a highpressure interconnection technique suited for large formats and numbers. This fabrication innovation assumed shape in the new numbered-up microstructured pilot reactors as depicted in this catalogue. IMM is well versed in catalyst optimisation and coating.

Thus, as desired from the requirements of the customer functionalisa tion of the microstructured reactor can be supplied which is the key to performance improvement of many chemical reactions. Process windows which are far away from usual practise are often tailor-made to optimal micro processing – prolific soil on no man‘s land. The afore mentioned improved high-pressure operation and the use of special materials for high temperature applications are just two reactor construction measures in this direction. Fill in the blank and knocking at the door to new applications Besides a holistic system-oriented approach, the catalogue simply needs to be steadily complemented bit by bit. This is done shoulder to shoulder with IMM’s new research and development directions. Although not all of these have already been solidified in the new catalogue and if so not to the same degree, the present portfolio has closed gaps and extends the range of application beyond chemistry.

• Micro processing architectures with modular building blocks for integration of mixing, reaction, and other operations • Separation and purification processes suited to continuous flow • New heating concepts (microwave) and solventless/-free processing (ionic liquids; supercritical fluids) • New applications: personal care, consumer goods, cosmetics, (functional) materials synthesis

It is our desire that the users of the tools in the catalogue will achieve as much process intensification as possible, hopefully exceeding what is needed and what was hoped – mirrorrotating the motto, largely known in the microreactor community and synonym for avoiding “white elephant’s directives “as much ‘micro’ as needed, not as technically possible”. Enjoy reading this new compendium and we appreciate if you contact us for discussion or inquiry at [email protected] or [email protected] +49-(0)6131-990 0. Volker Hessel Institut für Mikrotechnik Mainz GmbH

CONTENTS > superior products made by imm

Preface Contents Testing and quality control 01 Processes

Contents Kolbe-Schmitt synthesis Michael Addition Solvent-free thiophene bromination Synthesis of an imidazole-type ionic liquid Phenyl boronic acid synthesis (S)-2-Acetyl tetrahydrofuran synthesis Synthesis of intermediate for quinolone antibiotic drug Nitro glycerine production plant Brominations of aromatics and alkylaromatics Synthesis of an azo pigment dye, Yellow 12 Hydrogenation of nitrobenzene Direct fluorination of toluene with elemental fluorine Sulphonation of toluene Direct hydrogen peroxide synthesis out of the elements [4+2] cycloaddition of singlet oxygen to cyclopentadiene to make cyclopentene-1.4-diol Side-chain photochlorination of toluene-2.4-di-isocyanate 02 Plants

1 3 4 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Contents Organic Synthesis Plant Impinging-Jet Microreactor Plant for Precipitation Reactions Cream and Emulsification Plant Modular Microreactor Systems for Production Plants Falling Film Micro Reactor Plant Gas Phase Reactor Test Plant Fuel Processor Demonstration Plant Mixer-Settler Continuous Work-Up Plant 03 Components

Contents Overview applications Mixing principles Liquid/Liquid and Gas/Liquid Mixers or Reactors Special Gas Liquid Reactors Gas Phase Reactors Heat Exchangers 04 Annex

25 26 28 30 32 34 36 38 40 42 43 44 45 46 58 68 76 84

General terms and conditions of sale References

84 87

3

TESTING AND QUALITY CONTROL

4 Testing and quality control of IMM micro reactor devices and plants

People often complain that innovations need too much time and consume too much money until they are available for industry and society. This catalogue makes the first move to bring novel and highly innovative products for chemical micro process engineering to the customer. IMM regards such off-the-shelf delivery as indispensable to enable a technological break-through. The catalogue comprises both off-theshelf products and demonstrators that are ready for supply according to customers needs. IMM is aware that despite the novelty of the devices, they have to fulfil the demands of industrial processing. For this reason, we do not only invest in scientific and technological promotion of our devices, but also in quality control, improvement of robustness, supplying proper fluid connections, etc. First of all, our Quality Assurance policy is realised by a Quality Management System certified according to DIN EN ISO 9001. For reasons of transparency the following specific technical quality features are given additionally on the backside of each micro device‘s description in the catalogue: • Specifications • Options • Performance Data • Applications & References

Specifications

tion channel platelets made of various materials, or incorporation of specialty functions (e.g. of an inspection window).

As we know, you do not have much time until you need to set work on your measurement or processing. Our delivery times try to match our time demand to fabricate a small series or even individual pieces only as well as your wish to start work as soon as possible.

For this reason, devices are regularly controlled by inhouse leakage rate tests. IMM thereby applies known and recommended procedures for leak testing of large-scale apparatus which are modified to the needs of microflow devices. The setting of these tests orients on ASME and EU standards on leakage testing. If needed, leak tightness will be measured at elevated pressures and temperatures. The result will be expressed in the well-established way to classify leakage classes, e.g. as L0.01. In selected cases, more data are summed up in a graph in our assembly manual.

Performance Data

Performance characterization

Performance Data include information on temperature and pressure stability, leakage rates, applicable flow rates, residence times and more, all based on experimental evidence. This enables you to judge whether the device meets basic requirements of the process or not. Said data are supplemented by geometric parameters comprising information on internal volumes or surfaces, in absolute terms or as specific properties. In addition to these basic, material- and construction-based parameters, more detailed information on processing is given, including description of hydrodynamics such as flow patterns or interfacial areas for selected parameter sets. Reaction engineering data such as conversions or space-time yields may be given as well. Any further information that is relevant and not included for reasons of limited space is referred in „Applications & References“.

IMM aims at disclosing the functioning of its devices largely as well as at showing their limits. Our devices can act as multi-purpose tools for a diversified range of applications. The information on these applications result from own or by partners practised chemistry as well as disclosed customer processes.

Delivery Time

This is your guideline for your check on material compatibility and fit into existing environment (e.g. by comparing outer dimensions). Relevant dimensions are listed here.

From all these contents of Performance Data, three presently important aspects are exemplarily discussed more in detail below.

Options

Leakage rate tests

Since different customers have different demands on how a reactor might fit best to their intended application, materials, internal dimensions or simply fluidic peripherals may need to be changed. IMM tries to serve such demands on customized solutions. For instance, we typically offer a variety of, e.g. different fluid connectors, reac-

Our devices meet the requirements of complex, detailed analyses and should not only be suited for making snapshots on feasibility. Here, leak tightness at the best possible rate is absolutely essential for correct balancing of all streams and avoiding contamination of the environment.

Beyond multi-functionality, we identified application-unique uses for the micro devices and, vice versa, produce more and more custom-designed tools. Their functioning indeed can be thoroughly characterised and must be benchmarked to known apparatus and techniques. In this context, IMM runs several test set-ups, e.g. to characterise mixing, heat exchange, evaporation, and reaction processing. Besides such in-house testing, the first basic versions of the devices were usually tested by partners or third parties being experts in the field of the micro device‘s application. This particularly provides an independent assessment – either from the industrial or scientific point of view – concerning the performance of the devices. The results are documented in many peer-reviewed publications which are referred in the respective device‘s description.

Development of measuring techniques

IMM does not only use state-of-the-art measuring techniques for device performance characterisation but also actively develops new techniques that

5 are considered to comprise the essential information for the customer. In this context, we would like to point out that IMM was the first to suggest an advanced mixing test procedure for flow-through devices (besides simple visual inspection of colouring/  neutralisation) by modification of an approach used for batch apparatus originally, developed by the Villermaux group in Nancy, France (Ind. Eng. Chem. Res. 38, 3 (1999) 1075-1082).

Experimental Determination of Mixing Performance of Microfluidic Devices by the “Villermaux/Dushmann method”

Mixing has a decisive impact on the overall performance of microreaction processes. A large number of micro mixers using different functional principles is available in the meantime. Therefore, there is an increased need for measuring and comparing mixing performance. IMM tests its micro mixers with regard to mixing performance experimentally using the so-called “Villermaux/Dushmann method”. The determination of mixing performance by the Villermaux/Dushman method is based on the competition of two parallel reactions. The acid-catalysed reaction of potassium iodide with potassium iodate to elemental iodine competes with the faster neutralisation of the acid by a borate buffer-system. Relevant chemical formulas: + H2BO3 + H ➞ H3BO3 (very fast) + 5 I + IO3 + 6 H (fast)

➞

3 I2 + 3 H2O

I2 + I ➞ I3 (detectable by UV/Vis spectroscopy) In the experiments a buffered solution of KI/KIO3 is mixed with diluted sulphuric acid. In case of ideal mixing the acid is only consumed by the fast neutralisation. However, if mixing is less ideal iodine is formed by the comproportionation reaction. The formed iodine can be then detected as triiodide complex by UV-Vis spectroscopy with absorption band centred at 286 and 353 nm. The more iodine is detected the less ideal is the mixing perfomance.

IMM uses the chemical protocol described by S. Panic et al. (Chem. Eng. J. 101 (2004) 409-419). In the following the concentrations and preparation of the two solutions, pumped in the experiments at a volumetric flow rate ratio of 1:1 is given: Solution 1: A sulphuric acid solution with c(H2SO4) = 0.030 mol/L. Solution 2: A solution of KI, KIO3, NaOH, H3BO3. This solution was prepared directly in front of the experiments by mixing the following two solutions in a volumetric ratio of 1:1: Solution 2a: c(KI) = 0.0319 mol/L c(NaOH) = 0.0909 mol/L c(H3BO3) = 0.0909 mol/L Solution 2b: c(KIO3) = 0.00635 mol/L c(NaOH) = 0.0909 mol/L c(H3BO3) = 0.0909 mol/L

Applications & References

Information that is missing in the product sections might be found in the citations. You can be sure that the list of citations comprises the latest and most relevant information available on IMM‘s micro devices. Means, we limited this list to most relevant books and reviews.

PROCESSES

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01

CONTENTS > processes made by imm

Processes

Kolbe-Schmitt synthesis

8

Michael Addition

9

Solvent-free thiophene bromination

10

Synthesis of an imidazole-type ionic liquid

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Phenyl boronic acid synthesis

12

(S)-2-Acetyl tetrahydrofuran synthesis

13

Synthesis of intermediate for quinolone antibiotic drug

14

Nitro glycerine production plant

15

Brominations of aromatics and alkylaromatics

16

Synthesis of an azo pigment dye, Yellow 12

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Hydrogenation of nitrobenzene

18

Direct fluorination of toluene with elemental fluorine

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Sulphonation of toluene

20

Direct hydrogen peroxide synthesis out of the elements

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[4+2] cycloaddition of singlet oxygen to cyclopentadiene

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to make cyclopentene-1.4-diol Side-chain photochlorination of toluene-2.4-di-isocyanate

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KOLBE-SCHMITT SYNTHESIS

8 Motivation and Results

01

Low pressure operations under reflux conditions are typically favored for laboratory flasks and agitated tanks. Accordingly, the maximum temperature of many organic routes is often simply defined by the solvent boiling point. Micro reactor rigs on the other side allow a simple operation of liquid phases under high pressures and high temperatures. For instance, a system pressure of 50 bar is enough to maintain single-phase operation (i.e. no gas content and no boiling) even at temperatures up to 100°C higher than boiling points of typical solvents. This has been termed high-p,T processing. The faster operation at higher temperatures typically is paid by more side and consecutive

Applied Process Parameters • Pressure: 40 – 80 bar • Temperature: 100 – 220°C • Reaction time: 4 – 390 s

Benefits through Process Intensification • Increase in space-time yield by factor 440 • Increase in productivity by factor 4 • Possibly circumventing the more tedious original KolbeSchmitt route with autoclave operation and aggressive earth alkaline hydroxide bases

reactions. Thus, efficient mixing and shortening of residence time to the kinetically limit become important drivers for process optimization. For the aqueous-based Kolbe-Schmitt synthesis with resorcinol and phloroglucinol shortenings in reaction time by orders of magnitude (up to a factor of 2000) were achieved in this way. This benefit is counterbalanced by thermal degradation of the reactants and the products, in particular by decarboxylation of the 2,4-dihydroxy benzoic acid (see scheme below) and 2,4,6-trihydroxy benzoic acid.

MICHAEL ADDITION

9 Motivation and Results The merit of high-p,T processing (see initial chapter and under Kolbe-Schmitt synthesis for definition) was investigated for six Michael additions of two α,β-unsaturated carbonyl compounds and three amines. Extended processing times of up to 48 hours were reduced in this way down to a few minutes. The duration of the batch processing times is here much larger than kinetically needed to avoid too large heat releases and therefore the reactant is added drop by drop (see also “all-at-once“ procedures).

Applied Process Parameters • Pressure: 3 – 20 bar • Temperature: 20 – 90°C • Reaction time: 2 – 30 min

Benefits through Process Intensification • Reduction of reaction time from 24 h (batch) to a few minutes • Increase in space-time yield by factor 650 • Increase in productivity by factor 4 • Yields up to 99%

In addition, effects of higher temperature are given, since the reaction is carried out at much higher temperatures than the boiling points of the amines. For example, for the diethyl amine with a boiling point of -55°C, best operation was at 100°C, while the experiments were extended up to 200°C. Reaction times and consequently space-time yields were reduced by order of magnitude in this way. Yields of up to 99% at about full selectivity were achieved.

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SOLVENT-FREE THIOPHENE BROMINATION

10 Motivation and Results

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In batch processing aggressive reactants typically are diluted to prevent thermal overshooting and runaway. Even then they often are added slowly drop by drop to allow heat transfer to be adjusted to heat release. In some cases, this may take a long time, up to hours. This unnecessarily prolongs processing time and also the reaction then is carried out for a considerable part under totally changing reactant concentrations (from zero to full-load content). On the contrary, microstructured reactors with their efficient heat and mass transfer have the potential to contact the full reactant load “all-at-once“. In addition, micro reactors can cope with concentrated solutions or even pure liquid reactants. There are several examples known that such “all-at-once“ or solvent-free procedures are feasible in micro reactors with reasonable selectivity, whereas the same contacting led to vigorous reactions and even explosions (when done under special safety precautions with miniature volumes).

Applied Process Parameters • Pressure: 1 bar • Temperature: -10 – 0°C • Reaction time: A few ms

Benefits through Process Intensification • Continuous process with flexible output at constant selectivity of 80% • Use of pure bromine, decomposed at the spot • Simple control over substitution degree

The bromination of thiophene investigated used pure thiophene and pure bromine flows at temperatures from -10°C to room temperature. The micro reactor operation led to yields of 2,5-dibromothiophene up to 86%, at nearly complete conversion, which is better than for home-made (77% yield) and literature (50% yield) batch processing. Using the pure feeds and higher temperature, the reaction time was decreased from about two hours (for batch) to less than one second (for micro mixer reactor). Correspondingly, the space-time yields were by order of magnitude higher for the continuous micro reactor process. Due to the easiness to change reactant ratios and temperatures in the micro reactor rig, a fast parametric study could be done for finding optimal operating conditions.

SYNTHESIS OF AN IMIDAZOLE-TYPE IONIC LIQUID

Motivation and Results A variant of the novel chemistry concept is to use solventfree processes with aggressive reactants which exhibit heattransfer sensitivity. The exothermic synthesis of an ionic liquid was carried out in this way in a micro reactor rig, and addresses especially the need for temperature control during the reaction, since too high temperatures will lead to formation of unwanted side products decreasing product quality which is already visually observable by the yellow colouring of the otherwise clear product. The challenge is further increased by favourably working without any solvents which is expected to result in temperature increase. The chemistry cannot be disclosed due to intellectual properties rights of the industrial user. Even under the advanced thermal control of a microstructured reactor, one can observe for a thermostat temperature of 50°C an increasing yellow colouring of the product, i.e. the formation of unwanted side products. This finding, however, can be explained by looking at the determined temperature profiles. Obviously, the reactor or the selected dimensions are not capable of removing reaction heat in a sufficient manner. In order to improve heat removal for the higher flow rates, an approach was to use finer structures, e.g. 1/16˝ tubes instead of 1/8˝ tubes. The smaller tubes, however, impose an increase of pressure drop which may become a limiting operational parameter. Therefore, the determination of temperature profiles becomes so important by locating the reactor section where smaller tubes have to be used and therewith to minimise the use of smaller

tubes to where necessary. As can be seen from the temperature profiles, the heat removal capacity of the 1/8˝ tubes is sufficient in large parts of the reactor, e.g. for a total flow rate of 3.48 ml/min beginning at a reactor volume of 15%. In the following, therefore the first two reactor sections where exchanged by 1/16˝ tubes with same internal volume as the replaced 1/8˝ tubes. Exemplarily, the obtained temperature profiles with such a set-up for a total flow rate of 3.48 ml/min are given in Figure 7 with the corresponding profile of the set-up with all 1/8˝ tube sections as comparison. The maximum temperature rise above thermostat temperature was reduced from 50°C to 10°C with this reactor modification, yielding a clearer product. For the highest flow rate (6.96 ml/min) the modification did not prevent hot spot formation, since a good portion of the reaction is occurring after the first two tube sections and therewith not affected by smaller dimensions in the first two tubes. With regard to production purposes based on these experimental results an adapted reactor concept for higher flow rates was derived. The micro reactor consists of a stack of platelets and heat removal is improved by integration of microstructured heat exchangers. The testing is now in preparation. Furthermore, the micro reactor rig was rebuilt in stainless steel allowing in future extending the investigations to other ionic liquid synthesis requiring higher temperatures and pressures.

Applied Process Parameters • Pressure: 1 bar • Temperature: 50 – 60°C • Reaction time: 1 – 4 min

Benefits through Process Intensification • Successful transfer of a batch process into a continuous one with in-line and realtime temperature monitoring • Controlled reaction albeit high exothermicity (about 100 kJ/mol) • Direct and one step contacting of the reactants in almost stochiometric ratio (“all-at-once“) • Reduction of processing time from a few hours down to 1 min • Side product formation – coloring of the product – considerably diminished

• Safety issues reduced – low control & automation expenditure to prevent thermal runaway with hazardous reactants • Modularity – flexibility for different IL syntheses • Easy scalability – short time-to-market • Small CAPEX costs at reduced plant footprint • Legislation – fast authority approval • High share of working loads as compared to plant shutdown

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PHENYL BORONIC ACID SYNTHESIS

12 Motivation and Results

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Mixing sensitivity is particularly pronounced for the class of organometallic reactions. Often these reactions are carried out under cryogenic conditions to get acceptable yields. This can be changed when using microstructured reactors. In this way, the phenyl boronic acid synthesis from phenyl magnesium bromide could be performed at high selectivity

Applied Process Parameters • Pressure: 1 bar • Temperature: 50 – 60°C • Reaction time: 6 – 120 s

Benefits through Process Intensification • Increase of yield of pure product by 25% • Decrease of impurity level of crude product by factor 5, from 5% to 1% • Process simplification: Eliminating the distillation step • Favourable room temperature operation instead of cryogenic one • Better costing of micro reactor process: Less invest (no distillation column), less energy consumption, less waste disposal

even at room temperature. The yield was raised by about 25% as compared to the industrial batch production process. Energy savings are both given by shifting the former cryogenic process to room temperature and by achieving a highly pure crude product, thereby rendering the former energy-consumptive distillation step unnecessary. Thus, having higher selectivity did not only affect the reaction itself, but also downstream purification.

(S)-2-ACETYL TETRAHYDROFURAN SYNTHESIS

Motivation and Results In the (S)-2-acetyl tetrahydrofuran (ATHF) synthesis, the Grignard reagent MeMgCl is very reactive and not easy to handle in large scale. The Grignard reaction can not only cause safety and hazardous problems at industrial scale, but there are also issues of chirality conservation. The α-hydrogen of the starting material is unstable under basic conditions, and consequently, racemization may occur. The optical purity of the micro reactor product was

98.4% as compared to 97.9% at batch level. Further, there are selectivity issues, i.e. an over-alkylation to tertiary alcohol must be avoided. Also, the individual impurity level must be less than 0.2%. The micro reactor impurity was 0.18% by minimization of back-mixing, while the batch impurity was 1.56%. Accordingly, with fine thermal and flow control, the productivity and economics of this process are increased.

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Individual impurity

Optical purity

Batch

1.56%

97.7%

MRT

0.18%

98.4%

Applied Process Parameters • Pressure, Temperature, Reaction time: Not disclosed

Benefits through Process Intensification • With fine thermal and flow control, the productivity and economics are increased • Minimizing back-mixing during reaction reduces impurities by factor 8, from 1.56% to 0.18% • Chirality conserved during reaction

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S Y N T H E S I S O F I N T E R M E D I AT E F O R QUINOLONE ANTIBIOTIC DRUG

Motivation and Results

01

Five different types of reactors, including tube reactors, static mixers and a microstructured reactor, were tested for the synthesis of an intermediate to yield a quinolone antiTM biotic drug, named Gemifloxacin (FACTIVE ). Among several types of reactors investigated, the microstructured reactor was successfully applied to the synthesis of a pharmaceutical intermediate via a fast exothermic Boc protecting reaction step.

Applied Process Parameters • Pressure: 1 bar • Temperature: 15°C • Reaction time: Not disclosed

Benefits through Process Intensification • Micro reactor was the best out of 5 different reactor concepts, including conventional tube reactors and Kenics static mixers, with the figures of merit being maximal yield and temperature close to ambient • 97% yield

The reaction temperature was isothermally controlled at 15°C. By using the microstructured reactor the heat of reaction was completely removed so that virtually no byproducts were produced during the reaction. Conversions as high as 96% were achieved. The micro reactor operation can be compared with other reactors, however, which need to be operated at 0°C or -20°C to avoid side reactions.

N I T R O G LY C E R I N E P R O D U C T I O N P L A N T

15 Motivation and Results A continuous nitro glycerine pilot plant with microstructured mixer/multi-tube reactors was installed at Xi’an site in China and was operated at a production rate of 15 kg/h nitro glycerine meeting all specs. A rough calculation for annual throughput gives a production rate of nearly 130 metric tons per year. Taking all reactants, i.e. fuming nitric acid, oleum and glycerine into account the total annual throughput is in the range of 900 cubic meters. The main challenge for such kind of plant is to ensure safety for all, even worst operational conditions. Therefore, all reactants must be pre-cooled before entering the microstructured mixer. Also the mixer itself is actively cooled by means of an integrated heat exchanger as well as the multitubular reactor. Advanced simulations were made to solve the problems with equipartition volume flow through the multi-tube reactor and some new, specific micro-macro

Applied Process Parameters • Pressure: 1 bar • Temperature: 30 – 40°C • Reaction time: Some min

Benefits through Process Intensification • Nitro glycerine production (15 kg NG; > 100 l/h solution) • Manufactured nitro glycerine 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 and closed water cycle

interconnects for fluid-flow guidance were developed and integrated. The plant is comparably small and thus, the necessary space for the plant in a safe environment, e.g. a bunker, can be reduced. The manufactured nitro glycerine will be used as medicine for acute cardiac infarction. Therefore, the product quality must be on highest grade, and the test runs indeed revealed higher selectivity and purity. The plant could be operated safely; one of the next targets is to have it fully automated. As a second step, a plant for downstream purification by washing and drying the nitro glycerine, of notably larger size and complexity as the reactor plant, is going to be developed and currently under negotiation. Environmental pollution should be excluded by advanced waste water treatment. In a final stage, the micro reactor nitro glycerine plant may also encompass formulation and packaging.

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B R O M I N AT I O N S O F A R O M AT I C S A N D ALKYLAROMATICS

Motivation and Results

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The bromination of meta-nitrotoluene is an example for a high-temperature, high-pressure (high-p,T) side-chain bromination of alkylaromatics. The transformation from batch to continuous processing, the safe operation with bromine at temperatures over 170°C and the decrease of reaction time, respectively increase of space-time yields, were drivers for the development here. Molar ratios of bromine to m-nitrotoluene ranging from

Applied Process Parameters • Pressure: 15 bar • Temperature: 170 – 230°C • Reaction time: 2.6 min

Benefits through Process Intensification • Process simplification: Thermal process instead of photochemical one • Energy savings for the latter reasons • Solvent-free process with pure bromine • Considerable speed up of reaction by high-p,T operation • Quenching of non-reacted bromine on-line and instantly after use

0.25 to 1.00 were applied. The reactants were contacted in an interdigital micro mixer followed by a capillary reactor. At temperatures of about 200°C nearly complete conversion is achieved. The selectivity to the target product benzyl bromide is reasonably high (at best being 85%; at 200°C and higher being 80%). The main sideproduct formed is the nitro-substituted benzal bromide, i.e. the two-fold brominated side-chain product.

SYNTHESIS OF AN AZO PIGMENT DYE, YELLOW 12

Motivation and Results By the use of microstructured mixers, pigment and other particle syntheses can be improved, since the well-defined and predictable mixing improves the preparation all the way from seed generation until particle agglomeration. In this way, finer particles with more uniform size distribution were yielded for the commercial azo pigment Yellow 12.

The particles formed in the microstructured mixer have better optical properties such as the glossiness or transparency at similar tinctorial power. Since the micro mixer made pigments have more intense colour, lower contents of the costly raw material in the commercial dye products can now be employed which increases the profitability of the pigment manufacture.

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Applied Process Parameters • Pressure: 1 – 2 bar • Temperature: 20°C • Reaction time: A few s

Benefits through Process Intensification • • • • •

Benefits through process intensification Increase of glossiness by 73% and Increase of transparency by 66% Better costing, since less raw material has the same effect Easy scaling out of powder synthesis, which otherwise may be complex

H Y D R O G E N AT I O N O F N I T R O B E N Z E N E

18 Motivation and Results

01

The hydrogenations of nitro aromatics have high intrinsic reaction rates, which however cannot be exploited by conventional reactors as they are unable to cope with the large heat releases due to the large reaction enthalpies -1 (500 – 550 kJ mol ). For this reason, the hydrogen supply is restricted, thereby controlling reaction rate. Otherwise, decomposition of the nitro aromatics or of partially hydrogenated intermediates can occur. The hydrogenations of nitro benzene over supported noble metal catalysts were investigated in a microstructured falling film micro reactor. For nitrobenzene hydrogenation, the overall mass transfer coefficient kLa was conservatively estimated (based on the film thickness in the middle of the channels) to be in the -1 range 3 – 8 s . As a comparison, for intensified gas liquid -1 contactors kLa can reach 3 s , but for bubble columns and -1 agitated tanks it does not exceed 0.2 s . A wide variation of preparation procedures for the palladium catalyst was tested. A sputtered palladium catalyst exhibited low conversion and large deactivation of the catalyst (60°C; 4 bar). The corresponding selectivity was also low. A slightly better performance was obtained after an oxidation / reduction cycle. Following a s teep initial deactivation, the catalyst activity stabilised at 2 – 4% conversion and at about 60% selectivity. After reactivation, selectivity

Applied Process Parameters • Pressure: 1 – 4 bar • Temperature: 60°C • Reaction time: 5 – 20 s

Benefits through Process Intensification • One of the first g-l-s processes reported in microstructured reactors • Process not benchmarked in detail to batch ones

approached initially 100%. As side products, all intermediates except phenylhydroxylamine were identified. For a UV-decomposed palladium catalyst, a conversion was found slightly higher than for the sputtered one. A similar spectrum of side products as for the sputtered catalyst was given. For an impregnated palladium catalyst, complete conversion was achieved and maintained for six hours. Selectivity decreased with time, but remained still at a high level. The best performance of all catalysts investigated was found for an incipient-wetness palladium catalyst. Having initially more than 90% conversion, a 75% conversion at selectivity of 80% was reached for long times on stream. The catalyst life-time or the four types of catalysts, prepared by different preparation routes, depends on the catalyst loading which is related to the preparation route. The larger the loading, the longer the catalysts could be used before reactivation. The four catalysts had the following s equence of life-time and activity: Wet impregnation > incipient wetness > UV-decomposition of precursors > sputtering Several reactivation routes of the used catalyst were tested such as dissolution of organic residues by dichloromethane or burning of them by heating in air. In this way, initial activity was recovered, thus regaining complete conversion.

D I R E C T F L U O R I N AT I O N O F T O L U E N E WITH ELEMENTAL FLUORINE

Motivation and Results One way of process simplification is to make molecular complex compounds out of much simpler building blocks (e.g. by multi-component one-pot syntheses like the Ugi reaction), at best directly out of the elements. Especially in the latter case, this is often quoted as “dream reaction“. Typically, such routes have been realised so far from hazardous elements, easily undergoing reaction, but lacking of selectivity. One example for this is the direct fluorination starting from elemental fluorine which was performed, e.g., with toluene. Since the heat release cannot be controlled with conventional reactors, the process is deliberately slowed down.

Applied Process Parameters • Pressure: 3 – 20 bar • Temperature: 20 – 90°C • Reaction time: 2 – 30 min

Benefits through Process Intensification • • • •

Reduction of reaction time up to ~ 1000 Increase in space-time yield by factor 10,000 Increase in productivity by factor 5 Single-step operation replaces tedious Balz-Schiemann route • Less waste generation • Less reactor investment and process simplification

While for this reason the direct fluorination needs hours in a laboratory bubble column, it is completed within seconds or even milliseconds when using a miniature bubble column, operating close to the kinetic limit. Favourable electrophilic substitution is achieved, showing that unselective radical paths are largely absent. The overall selectivity of this non-optimised process amounts to about 25%, not far from the total selectivity of all the Balz-Schiemann steps to achieve the same result. Waste reduction is less since a single step synthesis is undergone. Productivity is much higher, as demonstrated by the order of magnitude larger space-time yields.

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S U L P H O N AT I O N O F T O L U E N E

20 Motivation and Results

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Toluene is heated up to 40°C using a microstructured heat exchanger while at the same time liquid sulphur trioxide is heated up to 60°C in order to evaporate it. Nitrogen is further added so as to dilute the system and the stream is then passed into a separator with the purpose of removing any traces of liquid. Thus, a gas stream is allowed to flow through to a microstructured reactor where it reacts with the liquid toluene. As shown in reaction (1), sulphonic acid is produced here via the desired reaction step. At the same time, though, sul-phone (reaction (2)), a mixed anhydride and sulphonic acid anhydride are also formed by side reactions. Sulphone cannot be converted further but the mixed anhydride reacts in the residence time module with toluene and forms the desired product, sulphonic acid, as shown in reaction (3). To convert the sulphonic acid anhydride to sulphonic acid, a hydration step is required (reaction (4)). To achieve this, water is added to the reaction mixture after the residence time module. Up to date, the reaction has been carried out up until the residence-time module. The final hydration step has not

Applied Process Parameters • Pressure: 1 bar • Temperature: 40°C • Reaction time: 5 – 15 s

Benefits through Process Intensification • One of the first complex micro-flow process designs for a multi-step synthesis • Better para-isomer selectivity

taken place. Even so, first results are encouraging. In order to evaluate reaction conditions, the mole ratio of the two reactants, sulfur trioxide and toluene, was varied and the selectivity of the desired product (sulfonic acid) and of the by-products (sulfon and the anhydride mixture) was determined. Evidently, with increasing SO3 /toluene mole ratio, the selectivity of the undesired by-products decreases while the selectivity of sulfonic acid stays nearly constant. At a mole ratio of 13/100, the selectivity of sulfonic acid is approximately 80% while that of sulfone decreases to approximately 3% and that of the sulfonic acid anhydride to approximately 1.3%. The isomer selectivity was also determined to be 8.1% for the ortho-sulphonic acid, 1.5% for the meta-sulphonic acid and 90.4% for the para-sulphonic acid. From literature, at a SO3 /toluene mole ratio of 13.4, the selectivity of the orthosulphonic acid was 17.6%, of the meta-sulphonic acid 1.2% and that of the para-sulphonic acid was 81.2%. Thus the improvement of the selectivity for the para-sulphonic acid can already be seen from these results. Very recently also the last hydration step was executed successfully.

DIRECT HYDROGEN PEROXIDE SYNTHESIS OUT OF THE ELEMENTS

Motivation and Results Several examples were reported for conducting routes in the explosive regime. Among them and most prominent was the detonating-gas reaction, using pure hydrogen and oxygen mixtures. This stands for a direct route from the elements. With special catalysts hydrogen peroxide, and not water, is obtained as value product, avoiding the circuitous Anthraquinone process, used at industrial scale. Calculations of explosion limits clearly demonstrate that there is a considerable shift, when explosive reactions are carried out in micro channels. The safety is not only related to avoiding thermal runaway, but relates to mechanistic reasons by breaking the radical chain by enhanced wall collision in the small channels with their large specific interfaces. Using this direct route to hydrogen peroxide, basic engineering for a new site for the production in the order of about 150,000 t hydrogen peroxide per year was done by UOP. Pilot processing and economic calculation of the production process has been performed. Based on microstructured

Applied Process Parameters • Pressure: 30 bar • Temperature: 50°C • Reaction time: A few s

Benefits through Process Intensification • Reduction of system pressure by factor 4, from 120 to 30 bar • Increase in space-time yield by 25%, from 1.5 to 2.0 g h/gcat • Favourable decrease in oxygen to hydrogen ratio by factor ~ 4, from 6.8 to 1.5 (OPEX costs) • Safe operation at all oxygen to hydrogen ratios in the explosive envelope • Full cost analysis for world-scale plant (162kMTA) with improved OPEX costing • 78% selectivity

mixing units, the new process is realised by direct contacting of hydrogen and oxygen (without inert gas) in the presence of a heterogeneous catalyst. The key to a high selectivity is to have a noble-metal catalyst in a partially oxidised state. Otherwise, only water is formed or no reaction is achieved. Peroxide testing at IMM used s uch a hydrogen peroxide selective catalyst placed within a mini-trickle bed reactor equipped with a micro mixer. Using UOP process specs, a space-time yield of 2 g hydrogen peroxide per g catalyst was achieved which exceeds literature values. In addition, operation at only 20 bar, considerably lower than for the published processes, and usage of smaller oxygen/  hydrogen ratios, saving valuable raw materials, is given. It could be clearly shown that improved selectivity and conversion is given at explosive oxygen/hydrogen ratios. UOP then carried out pilot-scale tests at other pressures in a fully automated explosion cell to reproduce vendor work and to study conditions and kinetics. A selectivity as high as 85% at 90% conversion was achieved so far (oxygen/hydrogen ratio of 1.5 – 3).

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[4+2] CYCLOADDITION OF SINGLET OXYGEN TO CYCLOPENTADIENE TO MAKE CYCLOPENTENE-1.4-DIOL

Motivation and Results

01

This reaction of industrial interest utilises singlet oxygen generated by irradiation in the presence of Rose Bengal. An endoperoxide is formed as intermediate which is converted to 2-cyclopentene-1.4-diol by reduction with thiourea. Due to the small length scales in micro reactors, e.g. 50 µm, high concentrations of a sensitizer may be used. As these materials typically have high costs, recycle loops with low inventory can be employed to consume only a low overall amount of sensitizer. The sensitizer absorption, despite the large molar extinction coefficient, is not over the tolerable limit since only small optical paths are employed. It is assumed that molecules in thin liquid layers face a broadly similar photon flux, unlike macro-scale photo processing.

Applied Process Parameters • Pressure: 1 bar • Temperature: 0 – 15°C • Reaction time: 5 – 20 s

Benefits through Process Intensification • • • • •

High quantum efficiency Safe on-site conversion of endoperoxides generated Reduction of energy consumption Use of high sensitizer concentration Reduced thermal overshooting of sample due to lowering light intensity

Low-intensity light sources should give efficient irradiation of thin liquid layers. Sample heating is reduced and so is radical recombination. In addition, oxygen-enrichment of solutions before and after micro reactor passage can be handled differently and is no longer a major safety problem. For the oxidation of cyclopentadiene by singlet oxygen to 2-cyclopentene-1.4-diol a yield of 19.5% was found. The feasibility of safely carrying out the oxidation of cyclopentadiene by singlet oxygen to 2-cyclopentene-1.4-diol was demonstrated. The explosive intermediate endoperoxide was generated and without isolation used on-site for a subsequent hydration reaction.

S I D E - C H A I N P H O T O C H L O R I N AT I O N O F TOLUENE-2.4-DI-ISOCYANATE

23 Motivation and Results Side-chain photochlorination of toluene isocyanates yield important industrial intermediates for polyurethane synthesis, one of the most important classes of polymers. The motivation for micro channel processing stems mainly from enhancing the performance of the photo process. Illuminated thin liquid layers should have much higher photon efficiency (quantum yield) than given for conventional processsing. In turn, this may lead to the use of low-intensity light sources and considerably decrease the energy c onsumption for a photolytic process. Due to the planar layer structure of most micro reactors a uniform illumination is yielded in addition, which can be kept when increasing throughput by numbering-up. Here, the individual reaction units are assembled in parallel again on a plane, only a larger one.

Applied Process Parameters • Pressure: 1 bar • Temperature: 130°C • Reaction time: 5 – 15 s

Benefits through Process Intensification • • • •

High quantum efficiency Increased selectivity, 79% instead of 45% for batch Increased conversion, 81% instead of 65% for batch Increased space-time yield by two orders of magnitude, 401 mol/(l h) instead of 1.3 mol/(l h) • Reduction of energy consumption • Reduced thermal overshooting of sample due to lowering light intensity

By using a nickel plate, space-time yields up to 401 mol/(l h) were achieved in the Falling Film Micro Reactor. Control experiments in a batch reactor at 30 min reaction time resulted in a space-time yield of only 1.3 mol/(l h), hence are by orders of magnitude smaller. By using an iron plate, spacetime yields up to 346 mol/(l h) were achieved in the Falling Film Micro Reactor. Conversions from 30% to 81% at selectivities from 79% to 67%, respectively yields from 24% to 54%, were found when using a Falling Film Micro Reactor (4.8 – 13.7 s; 130°C). Control experiments in a batch reactor (30 ml reaction volume) at 30 min reaction time resulted in a conversion of 65% at 45% selectivity, hence having a selectivity which is higher by about a factor of 2.

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PLANTS

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CONTENTS > plants made by imm

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Plants

Organic Synthesis Plant OSBP

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Impinging-Jet Microreactor Plant for Precipitation Reactions IJMP

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Cream and Emulsification Plant CSBP

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Modular Microreactor Systems for Production Plants

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Falling Film Micro Reactor Plant FFMR-BSP

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Gas Phase Reactor Test Plant

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Fuel Processor Demonstration Plant

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Mixer-Settler Continuous Work-Up Plant CWUP

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ORGANIC SYNTHESIS PLANT

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OSBP

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OSBP for 2-step reaction

Principle In micro reactor literature, the most frequently used approach for organic synthesis is the micro mixer/tube reactor. The organic synthesis bench-scale unit relies on this concept and has in addition control and measuring functions. It is based on the reliable hybrid concept of IMM, utilizing innovative micro reactor components in connection with well-proven conventional small-fluidic equipment. IMM has gained huge experience with carrying out organic reactions e.g. ethoxy silylations, metal-organic syntheses, and epoxidations in such micro mixer/tube reactor bench-scale units. As a result this unit concept was developed and tested to yield the bench-scale unit actually offered now. It comprises two pre-heating loops (as option: microstructured heat exchangers), a micro mixer, a 5/2-way valve, and 4 delay loops of different length collected to one outlet which allows to change the residence time for a given set of parameters during the reaction by simply switching the valve. On demand, the general bench-scale unit concept can be modified towards more complex design. The concept is amenable to supercritical processing as well.

OSBP for single-step reaction (top  view) 

OSBP for single-step reaction (inside  view) 

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Typical flow charts for Organic Synthesis Plant 

Operating Conditions Temperature (°C)

-50 – 180

Pressure stability (bar)

30 for stainless steel 3 for PTFE

Flowrate (l/h)

0.05 – 2.5 for mixer SIMM-V2 2.5 – 30 for mixer CPMM-V1.2-R600/12

Residence time (s)

4 changeable delay loops have a different length of approx. 1%, 5%, 20% and 100% (the absolute lengths will be adjusted to the applied mixer to yield reasonable residence times)

Leakage Class

L0.1

Further Applications Based on the IMM knowledge on general demands for a chemical synthesis plant, this basic set-up was designed. Though it should be directly applicable for many typical (organic) syntheses i.e. for gas/liquid or liquid/liquid mixing homogenuously or dispersing (emulsions, foams), even catalyst slurries might be processed. If the standard version is not sufficient, it might be differentiated and/or extended where needed, e.g. for multi-step processing. Insofar, this set-up represents a versatile tool to directly enter into micro chemical process engineering.

Specification of the Basic System • 2 pre-heating loops (as option: Microstructured heat exchangers) • 1 SIMM-V2-mixer or 1 CPMM-mixer with housing material stainless steel • 4 delay loops with different residence times, switchable online via a 5/2-way valve • 1 tube-in-tube heat exchanger (as option: Microstructured heat exchanger) at the outlet • All above devices mounted on a metal plate • Assembled set-up fits into a heating bath

Options • • • •

Temperature and pressure measurement unit Pumping units Process control unit, programmed in LabView Other materials on request

Pilot-scale plant for nitro glycerine production

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IMPINGING-JET MICROREACTOR PLANT F O R P R E C I P I T AT I O N R E A C T I O N S I J M P

28 Main part of the IJMP with mixing  chamber and heat exchangers 

02

The balance system for mass flow  control combined with gear pumps as  well as the process control system is  not shown here 

Principle The Impinping-Jet Microreactor Plant IJMP is the logical advancement of the Organic Synthesis Bench-Scale Plant OSBP for precipitation reactions which cause blockage by main or side products and cannot be processed in our standard OSBP. The delay loop was removed and the remaining blocking sensitive part, the mixer, substituted by the simplest nonfouling component for continuous mixing-processing, the Impinging-Jet Micromixer IJMM. Educt streams are tempered via two microstructured heat exchangers HX204 before entering the mixer, enabling a fast and efficient temperature control.

The overall pressure and temperature stability is mainly limited by the windows and gasket of the mixing chamber. The position of the IJMM in the mixing chamber can be adjusted in the vertical direction which allows best fitting connection of an outleaving (reaction) tube downstream, in case the mixing section tends to spraying causing contamination of the mixing chamber. Additional (inert) gas flushing is integrated. Another option is to use the Separation Layer Interdigital Micromixer SLIMM instead of IJMM to carry out precipitations.

29 nitrogen

nitrogen

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thermostat

The mixing chamber with height-adjustable IJMM inside  The process control system of the Impinging-Jet Microreactor Plant IJMP allows for both educt flows the exact mass flow regulation with gear pumps and balances as well as measuring and controlling their inlet temperature into the mixing chamber. Besides complete data acquisition including system pressure this LabView-based system can run given programs (e.g. overnight experiments) easily compiled with the integrated program editor. The collected data are as ASCII-files easily importable e.g. into Excel for further use.

nitrogen

Flow chart of the IJMP including balance system

Technical Data Name

Impinging-Jet Microreactor Plant

Order number

IJMP

Size (L x B x H)

main part depicted left: approx. W 50 cm x H 80 cm x D 30 cm

Connectors (Inlet/Outlet)

1/4˝ / 1/4˝

Standard material

Housing, mixer: 1.4571 Glass

Standard mixing channels (µm)

depending on used mixer, typically for IJMM: 350 µm diameter

Options

Other materials like Hastelloy, Monell or Titan on request

Operating Conditions Temperature (°C)

-200 °C to + 250 °C @ 1 bar

Pressure stability (bar)

0 - 40 bar @ 25 °C

Flowrate (l/h)

depending on used mixer, for IJMM-350 e.g. 1.4 – 3.0 l/h watery flow

The LabView-based process control system for the IJMP 

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C R E A M A N D E M U L S I F I C AT I O N P L A N T CSBP

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Cream Synthesis Bench-Scale Plant for 5 different chemicals 

Principle Generating emulsions is typically a process where all materials are being balanced or measured, placed in a flask or vessel and then vigorously stirred or homogenised with high energy consumption. Micromixers insofar proved in literature to reduce energy input by factor 10. Besides, more narrow droplet size distribution can be achieved within a shorter time as conventional techniques as only passing once through within milliseconds yields the result. Further taking the advantage of small hold-ups despite the pilot-scale productivity, a versatile tool concept is offered herewith enabling even a fast change of cream recipes within less than a minute. Respectively, a multitude of different pastes, creams, lotions within short time can be produced as samples or in larger amounts. The CSBP-Demonstrator is based on the reliable hybrid concept of IMM, utilizing innovative microreactor

components in connection with wellproven conventional small-fluidic equipment. Respectively, small gear ring pumps for max. to 1 – 15 l/h depending on type and 140°C are used to convey up to 4 liquids and 4 solids being molten in the comprised heat bath into a mixer array as the 8 Component Caterpillar Micromixer (8CCPM) directly yielding the hot emulsion. The 4 solid components can be fed via temperature-controlled heated funnels into tempered flask whereof being pumped, enabling a full continuous processing even in case of production need. The liquids are heated up with simple heating loops, bath-fed or electrically driven heat exchangers depending on total flow rate need. The general bench-scale unit concept can be modified towards more complex design. The concept is amenable to unusual processing as well.

Cream Plant positioned on a holder  for easy maintenance, cleaning and  device exchange 

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Cream Synthesis Plant for 1 solid and 1 liquid educt and  continous use 

02 Operating Conditions Temperature (°C)

20 – 140

Pressure stability (bar)

20 for stainless steel 3 for PTFE

Flowrate (l/h)

2.5 – 60

Leakage Class

L0.1

Specification of the Basic System • Up to 8 electrical pre-heating storage tanks • Eightfold-CPMM-mixer with housing material stainless steel or PTFE • Micro annular gear pumps • All above devices mounted on a metal plate • Assembled set-up fits into a heating bath

Options • Temperature and pressure measurement unit • Process control unit, programmed in LabView • Other materials on request

Array of 3 CPMM to mix 4 components nearly at  once, 4CCPM, ca. 3-60 l/h

Seven CPMM structures to mix  8 components, of PMMA, 8CCPM 

Special StarLaminator10, to mix  3 components at once, ca. 5-80 l/h

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MODULAR MICROREACTOR SYSTEMS FOR PRODUCTION PLANTS

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Exemplary basic unit of a Modular Microreactor System consisting of distributor, distributor, three reaction modules and collector 

Principle Recent R&D efforts led to the development and realisation of modular microreactor based systems for production plants. The concept was developed to execute reactions which benefit from the outstanding properties of microstructured devices, especially concerning heat transfer and mixing. Mainly for fine and specialty chemistry reactions the size of the modules allows scaling up processes up to the production scale. The basic unit thereby consists of newly developed, flangeable modules made of stainless steel. The modules are manufactured of vacuum brazed microstructured plate stacks which can withstand higher pressures. Each basic unit is composed of a distributor module

which spreads the feed stream to all channels of the stack, a variable number of reaction modules with integrated heat exchanger function and a subsequent collector module. Each module can be tempered on its own temperature level if required. This basic unit can then be extended to an overall modular system following the multiscale approach, e.g. the microstructured modules can be followed by a mini-scale multitube reactor which exhibits sufficient heat transfer properties to complete the reaction. The basic units can furthermore be supplemented with microstructured heat exchangers, e.g. of the HX or WT series, and micromixers, e.g. of the CPMM-V1.2 or of the StarLam series.

Configuration with heat exchangers  (HX-series), tempered caterpillar  mixer (CPMM-V1.2-HEX) (CPMM-V1.2-HEX),, distributor distributor,, reaction module and collector 

33 reactant 1

heat transfer medium heat transfer medium

heat transfer medium

heat transfer medium

heat transfer medium

heat transfer medium

heat transfer medium

coolant

micro heat exchanger

micromixer heat transfer medium

distributor microstructured microstructured microstructured collector module reaction module reaction module reaction module module

micro heat exchanger

R(n+1) conventional micro heat (multi) tube exchanger reaction module

reactant 2 flangeable basic unit product

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Flow chart of a typical configuration of a modular microreactor system for production plants 

Operating Conditions (exemplary) Temperature (°C)

+ 200 °C @ 50 bar (higher temperature on request)

Pressure stability (bar)

50 bar @ 200 °C (higher pressure on request)

Flowrate (l/h)

depending on the reaction, module system e.g. 1 to 10 (more upon request)

02

4.0

Bo = 90

1.0

3.5 F(Θ)

3.0

0.8

2.5

   )

        )

      Θ 0.6

2.0

   (

   F

1.5

0.4 E(Θ)

      Θ

        (         E

1.0

0.2

0.5

0.0

0.0 0.0

0.5

1.0

1.5

2.0

Θ=t/τ[-]

Normalised residence time distribution function for a basic  unit with 2 reaction modules at 3 l/h flowrate 

Multi-tube module 

Vacuum brazed reaction module with open reaction Vacuum channels 

Distributor/collector module 

Basic unit and subsequent  multi-tube module 

FA L L I N G F I L M M I C R O R E A C T O R P L A N T

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FFMR-BSP

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Falling Film Micro Reactor Plant 

Principle The Falling Film Microreactor BenchScale Plant comprises besides the Falling Film Microreactor, a mass flow controller for the gas flow, a cryostat, a supply- and a withdraw-pump for the liquid flow. The precise assortment of the peripheral equipment components basically depends on the different chemical reactions which the customer wants to perform. This means, the general bench-scale unit concept can be modified towards more complex design.

Operation in the Falling Film Microreactor device can be performed up to 300°C at a pressure of max. 10 bar by using the standard version (upper housing with inspection glass) or max. 20 bar with the special upper housing without window. The suitable liquid flow rates depend on the channel geometry of the corresponding reaction plate and the property of the reactant (e.g. viscosity). For example, the max. liquid flow rate by using isopropanol and a channel size of 1200 µm x 600 µm is 1.5 l/h.

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02 Flow charts of a Falling Film Microreactor Plant 

Technical Data

Specification of the Basic System

Name

Falling Film Microreactor Plant

Order number

FFMR-BSP

Connectors (Inlet/Outlet)

1/4˝ / 1/4˝

Material of FFMR

1.4571 for housing and reaction plate copper for cooling plate borofloat glass for inspection

Standard mixing channels of FFMR (µm)

300 x 100 (64 channels) 600 x 200 (32 channels) 1200 x 400 (16 channels)

Options

Other materials like Hastelloy, Monell or Titan on request

Operating Conditions Temperature (°C)

180 (option 300)

Pressure stability (bar)

10 (without Borofloat glass: 20)

Flowrate (l/h)

0.05 for channel geometry 300 µm 0.6 for channel geometry 600 µm 1.5 for channel geometry 1200 µm

Residence time (s)

0.8 – 20

Liquid film thickness (µm)

25 – 100

Leakage Class

L0.01

• • • • • •

Falling Film Microreactor (FFMR) (FFMR) Flow controller for reaction reaction gas Supply pump for liquid reactant Withdraw pump for product Low temperature thermostat; cryostat respectively respectively Connecting tubes

Options • Mass flow controllers • Temperature and pressure measurement unit • Process control system

GAS PHASE REACTOR TEST PLANT

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Bench-scale catalyst evaluation unit for fossil and alcohol fuel processing 

Principle This bench-scale unit serves for investigations in heterogeneous catalysis with respect to fossil fuel and alcohol fuel processing, e.g. concerning the determination determinat ion of the activity/selectivity and stability of catalysts, as well as process optimization studies of this class of gas-phase reactions by fast serial variation of process parameters such as temperature, pressure, gas flow velocity, and gas composition. The bench-scale unit comprises commercial mass-flow controllers for control of the gas feed, flame arresters to stop flame propagation, and a microstructured evaporator fed by a liquid

tank, which produces steam or organic vapours (optional), all mounted on a metal board. Steam and gas feed are mixed and enter a micro device composed of two laser-welded microstructured platelets having one inlet and outlet tube, also welded to the two-platelet stack. Operation in the micro device can be performed up to 900°C at a pressure of 10 bars, using external resistance heating. The catalyst is usually introduced into the micro channels prior to interconnection, e.g. by the wash-coat route and subsequent impregnation. By laser-welding the thermal treatment is spatially confined

so that the catalyst is not destroyed during interconnection. The welded micro device can be cut after use so that analytical studies can be carried out with the catalyst layers that were exposed to the reactants during time on stream. Besides using the two-platelet stack micro reactor, any other IMM or othersource micro reactor can be integrated into this bench-scale unit. In this case, please contact IMM prior to the construction of the bench-scale unit so that the required modifications can be arranged.

37 In conjunction with bench-scale unit construction, IMM services include provision of a manual which contains, besides general information, detailed documentation on experiences gained with operation of this bench-scale unit. Exemplarily, operational modes are given so facilitating the first experimental steps when starting bench-scale unit operation. In case of further questions and desires, an IMM contact person can be consulted by mail or phone. By special request, a process parameter monitoring program based on the LabView software can be supplied that allows automatic acquisition of temperature and pressure data. The bench-scale unit was in detail investigated not only for numerous steam reforming and partial oxidation reactions of alcohol and hydrocarbon fuels, but also for CO clean-up such as water-gas shift, preferential oxidation and meth-

anation. Besides constructional changes in the set-up, this requires the coating of another catalyst. IMM has in particular gained experience in building bench-scale units for all kind of fuel processing unit operations and in operating respective micro devices. An extension of the use of benchscale units for other types of heterogeneous catalytic studies is principally possible and requires in most cases only minor modifications of the bench-scale unit construction. Here, information on the exact process desired is required from the customer and a special offer will be prepared by IMM. The performance of the reforming bench-scale unit was demonstrated in detail for propane steam-reforming, methanol and ethanol steam-reforming, partial oxidation of propane, water-gas shift at high and low temperature, preferential oxidation of carbon monoxide, and for the methanation of carbon monoxide.

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Specification of the Basic System • Mass flow controllers for hydrogen, nitrogen, hydrocarbons, carbon monoxide, carbon dioxide, air and water (choice of selection optional) • Stainless steel vessels for water and organic liquids • Evaporator • Valves, manometers, flame arresters • Temperature controllers • Pressure controller (optional) • All above devices mounted on a metal frame • Available IMM-reactors for testing catalyst performance

Options • Additional mass-flow controllers (e.g. for air, oxygen) • Additional periphery heating (pipes) • Additional liquid storage tanks (required for long term operation) • Additional temperature sensors

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F U E L P R O C E S S O R D E M O N S T R AT I O N P L A N T

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Test bench for single reactors and multiple reactor arrangements 

Principle This test bench serves for investigations in reactor performance testing with focus on fuel processing applications such as fossil and alcohol fuel reforming and catalytic CO-clean-up. The unit is designed for tests of startup, steady-state and transient reactor behaviour and for long-term tests. Process optimization studies may be performed, if serial combinations of several reactors (e.g. reforming, water-gas shift and preferential oxidation reactors) are integrated into the unit. Fast serial variation of process parameters such as temperature, pressure, gas flow velocity, and gas composition are possible.

The test bench comprises commercial mass-flow controllers for control of the gas feed, flame arrestors to stop flame propagation, and various evaporator types (evaporation power between 10 s of watts up to kilowatts). The evaporator, which is fed by a liquid tank, produces steam or organic vapour. All devices are mounted onto a metallic frame. Steam and gas feed are mixed and enter the reactor, which may be a microstructured device or a conventional reactor type (metallic monolith or fixed bed reactor). Operation in the microstructured reactors may be performed up to 900°C at pressures of up to 5 bars, for maximum temperature

of 500°C at pressures up to 100 bars, using either external resistance heating or integrated catalytic burners. Also internally cooled reactors (heat exchangers) and combinations of these reactor types may be tested in the test bench. By-pass lines are introduced, thus allowing for switching off the individual reactors under test. The catalyst is usually introduced into the micro channels prior to the sealing procedure (normally laser-welding), e.g. by the wash-coat route and subsequent impregnation. By laser-welding the thermal treatment is spatially confined so that the catalyst is not destroyed during interconnection.

39 Please contact IMM prior to the construction of the test bench so that the modifications required can be arranged. In conjunction with test bench construction, IMM services include provision of a manual which contains, besides general information, detailed documentation on experiences gained with operation of this bench-scale unit. Exemplarily, operational modes are given so facilitating the first experimental steps when starting bench-scale unit operation. In case of further questions and requests, an IMM contact person can be consulted by mail or phone.

Operating Conditions Max. pressure (bar)

10

Max. reservoir of water or organic liquid for one continious run (l)

20

Max. flowrate (gas) approx. (Nl/min)

about 500

Max. flowrate (liquid) approx. (g/h)

about 5000

Max. evaporator temperature (°C)

200

Specification of the Basic System • Mass flow controllers for hydrogen, nitrogen, hydrocarbons, carbon monoxide, carbon dioxide, air and water (choice of selection optional) • Stainless steel tanks for water and organic liquids • Evaporators • Temperature controllers • Pressure controller (optional) • Valves, manometers, flame arresters • All above devices mounted on a metal plate • Available Reactors

Options • • • •

Additional massflow controllers (e.g. for air, oxygen) Additional periphery heatings Additional liquid storage tanks Additional temperature and pressure sensors

By special request, a process parameter monitoring program based on the LabView software can be supplied that allows automatic data acquisition of temperature and pressure. The bench-scale unit was in detail investigated for steamreforming and autothermal reforming of fossil fuels, for water-gas shift and for the preferential oxidation of carbon monoxide, all up to the 10 kW range (lower heating value of the hydrogen produced/processed), however it may – on special customer request – be modified to allow for investigations of other types of heterogeneous gas-phase reactions. Here, information on the exact process desired is required from the customer and a special offer will be prepared by IMM.

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MIXER-SETTLER CONTINUOUS WORK-UP PLANT CWUP

40 Principle

02

Against the background of a twophase liquid/liquid reaction performed in a microreactor based set-up, IMM has developed a matching Continuous Work-Up Plant. This plant consists of a combination of mixers and settlers to cover the functionality of inital phase separation and of two washing steps with water for the organic phase. A biphasic reaction mixture (e.g. organic phase and aqueous phase) is separated by an initial, gravity driven mini-settler. In the next step, the organic phase is contacted with an aqueous washing phase via a Caterpillar Micromixer and separated subsequently in a second settler. In the third step, the s ame procedure is repeated. One settler-unit is composed of a glass tube, attached with special fittings on both ends. The flow of the organic phase in the two washing steps is automatically regulated by gear pumps based on the measurement by special filling level sensors. The water level in a settler is adjusted by a flexible tube siphon. A sensor is measuring the pH-value of the waste aqueous phase of the second washing step and thereby monitoring washing success of the organic phase. Based on this the flow rate of the aqueous phase is adjusted automatically.

CWUP; separation of an incoming biphasic system and subsequent 2-step  washing with micromixer-settler-siphon system.

Operating Conditions

Specification of the Basic System

Total flow rate

up to 150 ml/min

Operating pressure

atmospheric

Temperature

up to 80°C

• Three settlers (glass tube and siphons) • Two Caterpillar Micromixers • Two + two gear pumps • Four filling level sensors • Filling level-flow rate controller • Lab hood-like housing with transparent doors

41 distilled water

distilled water

inlet for biphasic reaction mixture

product

optional inlet for homogeneous reaction mixture

aqueous waste

aqueous waste

aqueous waste

Typical process flow chart for the Mixer-Settler Continuous Work-Up Plant 

1. settler 

pump 

mixer 

pump 

mixer 

2x sensor 

2. settler 

2x sensor 

3. settler 

pH-sensor 

Main components of the CWUP 

3x siphon system

Detail view on settling process (above); overview on plant  components for a double washing unit (left).

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COMPONENTS

42

03

CONTENTS > components made by imm

43

Components

Liquid/Liquid and Gas/Liquid Mixers or Reactors

Overview Applications

44

Mixing Principles

45

Caterpillar Split-Recombine Micromixer CPMM-V1.2 group class-R150, -R300, -R600, -R1200, -R2400 46 Star Laminator StarLam group class -30, -300, -3000, -30000

50

Slit Interdigital Micromixer SIMM group class SIMM-V2, HPIMM, SIMHEX, SSIMM

54

Liquid/Liquid Microreactor LLMR-MIX

58

SuperFocus Interdigital Micromixer SFIMM-V2

60

Impinging-Jet Micromixer IJMM

62

Special Gas Liquid Reactors

Falling Film Microreactor FFMR

64

Gas Phase Reactors

Gas Phase Microreactor GPMR

68

Gas Phase Microreactor with Mixer and Internal Heating/Cooling GPMR-Mix

70

Catalyst Micro Burner Reactor CMBR

72

Catalyst Testing Microreactor CTMR

74

Heat Exchangers

Laser-welded Micro Heat Exchanger WT-series

76

Brazed Micro Heat Exchangers HX-series

78

Tube Heat Transfer Micro Device THTMD

80

Laboratory Evaporator

82

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OVERVIEW

44

03

> applications

Applications

Type of Standard Mixers and Reactors

Application Examples

Liquid/liquid and gas/liquid reactions

SIMM, CPMM, StarLam, SFIMM-V2

• • • • • • • • • • • • • • • • •

Grignard reaction Kolbe-Schmitt synthesis Sonogashira couplings Formation of polyacrylates Formation of blockcopolymers Phenyl boronic acid synthesis Benzal chloride hydrolysis Dendrimer synthesis Michael reaction Nitro glycerine synthesis Bromation of alkylaromatics with elemental bromine Synthesis of (S)-2-Acetyl-tetrahydrofuran (antibiotic drug intermediate) Synthesis of an intermediate for TM Gemifloxacin (FACTIVE ) Isomerisation of allyl alcohols H-transfer reduction of citraconic acid ester Aromatic nitrations Aliphatic nitrations

Special gas/liquid reactions

FFMR, MBC, SIMM, CPMM and StarLam • • • •

Reactions at high pressure

HPIMM

• Alkylation of aromatics with supercritical CO2 • Direct H2O2 synthesis

Dispersion and emulsion formation

SIMM, CPMM, StarLam

• Mixing of silicon oil and water • Mixing of diesel and water

Mixing of liquids differing in viscosity

SFIMM-V2, SIMM, StarLam

• Addition reaction with liquid ethylene oxide synthesis

Photochemical reactions

Produced with window: SFIMM-V2, FFMR, MBR

• [2+2] Diels Alder photooxygenation of olefines • Photochemical chlorination of alkylaromatics

Reactions with catalytic suspensions

CPMM

• Hydrogenation of C=C double bonds

Inorganic particles

SSIMM, CPMM, IJMM, SLIMM

• • • •

Organic particles

SSIMM, CPMM, IJMM, SLIMM

• Bipyridine (precipitation) • Starch (dispersion + solidification)

Pigments

SSIMM, CPMM

• Azopigment Yellow 12 (precipitation) • Azopigment Clariant (precipitation)

Polymer particles

HPIMM, SSIMM, CPMM

• Polystyrene (dispersion + solidification)

Microcapsules

SSIMM, CPMM

• Model prot. PSA-in-LGPA (disp. + solid.) • Nanocomp. - Steroids (disp. + solid.)

Amphiphilic particles

SSIMM

• Stearate/phenofibrate (self-assembly) • Amphiphilic vesicles (self-assembly) • Block copolymer vesicles (self-as.)

Direct fluorination of toluene Sulfonation of aromatics Hydrogenation of nitrobenzene Hydrogenation of cinnamic acid esters

Particle and pigment synthesis

Titanates (precipitation) CaCO3 (precip.) Au (GNP), Pt/C (reduction) {N-doped TiO2 (hydrothermal process)}

> mixing principles by imm

  s   e    l   p    i   c   n    i   r   p    l   a   n   o    i    t   c   u   r    t   s   n   o    C

Recirculation Split-recombine

Ramp-up/down Bas-relief

  s   e   s   s   a    l   c    t   c   u    d   o   r    P

Caterpillar CPMM

Multi-lamination

Interdigital channel array

Slit

Triangular

Standard SSIMM

Super-Focus (V 2) SFIMM

Version 2 SIMM-V2 SIMM-V 2

Heat Exchanger SIMHEX   s    t   c   u    d   o   r    P

High-Pressure HPIMM

CPMM R150/12 (0,1l/h - 1,0l/h)

45 45

Jet collision

Interdigital disk array

Tilted jets

Star Laminator StarLam

Impinging-jet IJMM

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03

C AT E R P I L L A R M I C R O M I X E R

46

CPMM-V1.2 GROUP CLASS-R150, -R300, -R600, -R1200, -R2400

03

CPMM group class 

Principle The Caterpillar Micromixers are particularly suitable for applications where fast mixing at higher throughput is desired, providing highest performance for l/l-mixing as well as for g/l- or l/ldispersing. As they consist of a structured single channel, these devices may also be used successfully if precipitation occurs during the reaction or if fine slurries shall be processed. The higher flowrates enable production scales of a few up to about 100 tons per year with all the advantages of our micro mixers, such as mixing quality, availability of different housing materials and safety gains.

The Caterpillar Micromixer has internal bas-relief structures which induce recirculation flows transverse to the flow direction which result in efficient chaotic mixing. At very low Re numbers, e.g. for viscous flows at low flow rates, the mixing mechanism may change and a near-multilamellae type flow pattern arises which uses diffusion mixing in thin layers, in a split-and-recombine fashion.

Simulated “real“ flow profiles at high flow rates in Caterpillar Micromixers 

47 Single Caterpillar Micromixers

CPMM sizes, from left: R150, R300, R600, R1200, R2400 

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03 Caterpillar Micromixer Arrays & Stacks Research Topics at IMM  In the context of IMM´s efforts in the continuous advancement of our components for production purposes two prototypes of numbered-up versions of the CPMM-R600/12 mixer have been realized recently. They combine the unique properties of the Caterpillar Micromixers and their less clogging-sensitive structures with the aim to process higher throughputs. In the STACK-10x-CPMM-R600/12 ten caterpillar structures on plates are stacked and brazed

together allowing high pressure applications. This mixer has been successfully tested for a dispersion step with a throughput of up to 600 kg/h. In the ARRAY-16x-CPMM-R600/12 the caterpillar structures are arranged in a different manner requiring also a new feed distribution system but decreasing pressure drop. Development here has been accompanied by modelling works to learn and understand fluidic behaviour, mixing, and fluid equidistribution when numbering up.

C AT E R P I L L A R M I C R O M I X E R

48

CPMM-V1.2 GROUP CLASS-R150, -R300, -R600, -R1200, -R2400

Single Caterpillar Micromixers with straight outlet

03

CPMM with a straight outlet

CPMM with a straight outlet made of PP  

The Caterpillar Micromixers with straight outlet are particularly suitable for applications where fast mixing is desired though precipitation occurs during the reaction or if fine slurries shall be processed. Due to the construction principle only 30 bar system pressure can be applied, nonetheless enabling production of slurries containing up to some 100 kg per year of fine powders. These mixers consist of a single structured mixer channel with an adapted outlet.

As the emerging reaction fluid is not forced to leave the mixer via the 90° elbow flow configuration and in addition the rectan-gular mixer geometry is smoothly adapted to the round shape outlet tube, eddies can be prevented in this region and therefore fouling is diminished or even prevented. This effect can further be promoted by the application of suitable special housing materials as e.g. PTFE.

Technical Data Name

Caterpillar Micromixer R300

Caterpillar Micromixer R600

Caterpillar Micromixer R1200

Caterpillar Micromixer R2400

Caterpillar Micromixer R300straight outlet

Caterpillar Micromixer R600straight outlet

Caterpillar Micromixer R12 00straight outlet

Caterpillar Micromixer R2400straight outlet

Order number

CPMM-V1.2R300

CPMM-V1.2R600

CPMM-V1.2R1200

CPMM-V1.2R2400

CPMM-V1.2R300-so

CPMM-V1.2R600-so

CPMM-V1.2R1200-so

CPMM-V1.2R2400-so

Mixing principles

all: bas-relief, recirculation flow (chaotic)

Size (L x B x H)

60 x 45 x 20

60 x 45 x 30

60 x 45 x 30

79 x 45 x 30

51 x 45 x 20

51 x 45 x 30

51 x 45 x 30

70 x 45 x 30

Connectors (Inlet/Outlet)

1/16˝ / 1/8˝

1/8˝ / 1/8˝

1/8˝ / 1/4˝

1/4˝ / 3/8˝

1/16˝ / 1/16˝

1/8˝ / 1/8˝

1/8˝ / 1/8˝

1/4˝ / 1/4˝

Standard mixing channels (µm)

300 x 300

600 x 600

1200 x 1200

2400 x 2400

300 x 300

600 x 600

1200 x 1200

2400 x 2400

Standard material

1.4435

1.4435

1.4435

1.4435

1.4435

1.4435

1.4435

1.4435

Options

Heat exchanger function is possible; other materials like Hastelloy, Monell, Titan, PTFE or other plastics on request

Operating Conditions Order number

CPMM-V1.2R300

CPMM-V1.2R600

CPMM-V1.2R1200

CPMM-V1.2R2400

CPMM-V1.2R300-so

CPMM-V1.2R600-so

CPMM-V1.2R1200-so

CPMM-V1.2R2400-so

Temperature (°C)

-40 – 220

-40 – 220

-40 – 220

-40 – 220

-40 – 220

-40 – 220

-40 – 220

-40 – 220

Pressure stability (bar)

100

100

100

100

30

30

30

30

Flowrate (l/h)

0.5 – 4

2 – 40

4 – 80

15 – 250

0.5 – 4

2 – 40

4 – 80

15 – 250

Residence time (ms)

3.6 – 72

2.25 – 45

3.15 – 70.2

3.6 – 60

5.4 – 108

2.7 – 54

4.05 – 81

4.32 – 72

Inner volume (µl)

10

25

78

250

15

30

90

300

Max Viscosity (mPas)

100

100

100

100

100

100

100

100

Leakage Class

< L0.001

< L0.001

< L0.001

< L0.001

< L0.01

< L0.01

< L0.01

< L0.01

49 Single Caterpillar Micromixers with Heat Exchanger Function

CPMM-R2400/10-HEX-ss-wt assembled (left) and disassembled (right)  As an additional feature the Caterpillar Micromixers may be offered with an integrated heat exchange function particularly suitable for applications where pre-heating/  -cooling of the mixture is desired prior to the subsequent reactor (by means of e.g. heat exchanger delay loop) thus extending the application range to more exothermic reaction or application of molten materials. Of course, this heat exchange version may also be combined with the straight

outlet and its housing can be produced in nearby any material desired. Meanwhile, the Caterpillar Micromixers with heat ex-changer function are, notwithstanding the above photo of a gasketed one, typically brazed, turning the two heat exchange passages into service free units and enabling even for the gasketed center mixing section high system pressures and temperatures.

Multiple Caterpillar Micromixers

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03

8CCPM-R1200/8.7-PMMA For special mixing or dispersion applications, where no residence time/delay loop is needed, the Caterpillar Micromixers may be combined to arrays thus enabling a nearby simultaneous mixing of more than 2 fluids at once. With such arrays e.g. multi-component creams can easily be generated.

4CCPM-R952/8.2-R1200/8.1-ss-hplc  

STAR LAMINATOR

50

S TA R L A M G R O U P C L A S S - 3 0 , - 3 0 0 , - 3 0 0 0 , - 3 0 0 0 0

03

The StarLam family 

Principle The Star Laminators are the first real production tools of IMM for mixing purposes. They create an alternate, interdigital-type feeding array which is generated by stacking thin foils with star-like through-holes. In this way, a finely-dispersed injection of two fluid streams is achieved. The foil stack is inserted into the recess of a housing where it is tightened by applying compression.

The novel Star Laminators are largecapacity microstructured mixers 3 reaching volume flows up to the m  /h domain. The apparatuses yield at higher flow rates a mixing efficiency which compares the high performance of today’s low-capacity (l/h) micromixers. Therefore, continuity from the “real” micromixers over the herein described high-throughput tools to conventionally manufactured static mixers with even higher flow rates is given. A classification of the mixing efficiency versus the power input con-

firms this continuity as well. For the Star Laminator StarLam 3000 e.g. a 3 throughput of about 3 m  /h at a pressure loss of 0.7 bar was determined for watery sys-tems. In this way, the StarLam series expands the range of operation from pilot-scale microstructured mixers of the Caterpillar series into production applications.

51

StarLam 30000

StarLam 3000

StarLam 300

StarLam 30  

Technical Data Name

Star Laminator 30000

Star Laminator 3000

Star Laminator 300

Star Laminator 30

Order number

StarLam 30000

StarLam 3000

StarLam 300

StarLam 30

Mixing principles

Multi-Lamination

Multi-Lamination

Multi-Lamination

Multi-Lamination

Size (L x B x H)

220 x 425 x 480

95 x 95 x 150

40 x 40 x 64

40 x 40 x 64

Connectors (Inlet/Outlet)

DN 80/DN 50

DN 15/DN 25

8 mm/10 mm

8 mm/10 mm

Standard mixing channels (µm) 250

250

100

50

Standard material

Body: 1.4571 Foils: 1.4401

Body: 1.4571 Foils: 1.4401

Body: 1.4571 Foils: 1.4401

Body: 1.4571 Foils: 1.4401

Options

Other materials like Hastelloy, Other materials like Hastelloy, Other materials like Hastelloy, Other materials like Hastelloy, Monell or Titan on request Monell or Titan on request Monell or Titan on request Monell or Titan on request

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Operating Conditions Order number

StarLam 30000

StarLam 3000

StarLam 300

StarLam 30

Temperature (°C)

for FKM: -20 to +220 ; for FFKM : -20 to +315 ; for grap hite: -100 to +500 (old StarL am versi ons)

Pressure stability (bar)

100

100

100

100

Flowrate (l/h)

5000 – 30000

600 – 8000

80 – 1000

12 – 150

Residence time (ms)

180-1100

72 – 960

1.7 – 220

24 – 840

Inner volume (ml)

1500 (623 mix section)

160

5

2.8

Max Viscosity (mPas)

10000

10000

10000

10000

Leakage Class

< L0.001

< L0.001

< L0.001

< L0.001

STAR LAMINATOR

52

S TA R L A M G R O U P C L A S S - 3 0 , - 3 0 0 , - 3 0 0 0 , - 3 0 0 0 0

03

A B A Mixing channel

B

A

The feed plates of the StarLam series (here StarLam 3000), which are alternately stacked. A star-like plate serves for  fluid injection; another plate with circular conduit serves for  forming the mixing channel and separation of the plates. The plates of each layer are turned by 30° so that separate  feeds result.

StarLam 3000 foils during assembly on the assembly rods 

StarLam 3000

StarLam 30

StarLam 300

StarLam 30/300 disassembled 

Feed plates of StarLam 30, 300 and StarLam 3000 

Concerning the high flow rates used for practical applications, mixing occurs by turbulence. As to be expected, the StarLam apparatus cannot be used at very low flow rates, as simulations and reaction-type mixing experiments confirm. In this flow regime, a segregation of fluid layers is given so that mixing is here not effective enough. On the contrary, at high flow rates experimental characterization of mixing efficiency by using competitive reactions shows that by increased turbulent action an increasing mixing performance of the Star Laminators is reached which then compares with the high quality of the smaller micro mixers, supplied by IMM. When plotting mixing efficiency versus pressure drop it becomes evident that a continuity is given to the Caterpillar series, i.e. at the same pressure drop an equal mixing efficiency is yielded independent which microstructured mixer is chosen as to be expected for a turbulent mixing scheme.

stack, the StarLam series can be cleaned in a straightforward manner, e.g. if fouling was noted. The circular outlet channel has macroscopic dimensions so that also here particles will not be detrimental.

As for any microstructured mixer, the feeding section is most sensitive to particles and fouling. However, owing to their simple reversible assembly, which is a mounted foil

The foils of the Star Laminators are fabricated by laser cutting; the housing is made by precision machining. Due to the geometry of the StarLam a multicomponent mixing can be easily realised by re-allocating the 12 single holes, e.g. 2 educts via 2x6 holes (standard), 3 educts via 3x4 holes or 6 + 2x3 holes (cf. p. 53 detail in photo top left), 4 educts via 4x3 holes or… For such an application the conventional housing needs only other housing bottom parts as to feed those single holes accordingly. Despite the fact that such a 3-, 4- component housing can be easily rebuild as 2 component housing, the feeding of the educts can also be adjusted by the mixing foil thickness as to enable mixing ratios of up to 1:100. Finally, the housing of StarLam30 and StarLam300 are identical and those mixers vary only in height and inner geometry of the mixer foil stack.

53

StarLam for mixing 3 components at once, 3CSL

StarLam 30/300/3000 connected in a multi-testing pilot plant 

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SLIT INTERDIGITAL MICROMIXER SIMM GROUP CLASS SIMM-V2, HPIMM, SIMHEX, SSIMM

54

03

SIMM-V2

HPIMM

SSIMM SIMHEX

SIMM group class 

Principle This group class of micromixers is a classic amongst all IMM chemical micro processing products. It has been used by a large number of customers, is cited multiple times in literature, and is indeed one of our best sellers. They combine the regular flow pattern created by multi-lamination with geometric focussing which speeds up liquid mixing.

Due to this double-step mixing, the slit mixers are amenable to wide variety of processes such as mixing, emulsification, single-phase and multiphase organic synthesis. Extensive knowledge on hydrodynamics, mixing performance and reaction engineering for diverse applications of these mixers has been documented worldwide.

Interdigital flow passes slit to create  multi-lamellae 

Research Topics at IMM  One important task at IMM is the continuous advancement of our components for the use in production. The pictures here show our latest efforts for a 10-fold scaled-up version of the SIMM-V2 mixer (ARRAY-10x-Slit Interdigital Micromixer), combining the unique properties of the interdigital mixers and their small structures with the wish to process larger throughputs.

Ten mixing elements are operated in parallel using common feed structures. Two kinds of upper housings have been realised: One collecting all ten single outlet streams in one and one with ten separated outlets. The latter allows systematic equidistribution measurements. The device has been developed for a liquid/liquid dispersion step.

55 SIMM-V2

HPIMM

Individual parts of the SIMM-V2 device

Principle

Individual parts of the HPIMM  

Principle

This version has all the benefits of mixing using multi-lamination and focusing only. Deliberately avoiding volume expansion, the inner volume could be decreased to only 8 µl, coming along with improved fluidic connections, e. g. to pumps and tube reactors, as it employs HPLC connectors. Compared to the connectors of the standard version SSIMM, the HPLC joint to steel tubing improves leak tightness and higher pressure operation can be achieved.

Technical Data

This micromixer was optimized using a metal sealing for tightening the two parts of the housing. As a consequence, the limits of pressure and temperature during operation are much higher than for flat-seal tightened devices. The mixer also comprises expansion-free outlet channel geometry, i.e. renounces on jet mixing, but relies on multi-lamination and geometric focusing only.

Technical Data

Order number

SIMM-V2

Order number

HPIMM

Mixing principles

Multi-lamination

Mixing principles

Multi-lamination

Size (L x B x H)

30 x 40 x 30

Size (L x B x H)

25 x 21 x 37

Connectors (Inlet/Outlet)

1/16˝ / 1/16˝ HPLC

Connectors (Inlet/Outlet)

1/16˝ / 1/16˝ HPLC

Standard mixing channels (µm)

45 x 200

Standard mixing channels (µm)

approx. 45 µm x 200 µm

Standard material

Body: 1.4571 Inlay: 1.4435

Standard material

Body: 1.4571 Inlay: 1.4401

Options

Other materials like Hastelloy, Monell or Titan on request

Options

Other materials like Hastelloy, Monell or Titan on request

Operating Conditions

Operating Conditions

Temperature (°C)

-40 – 220

Temperature (°C)

-40 – 500

Pressure stability (bar)

100

Pressure stability (bar)

600

Flowrate (l/h)

0.04 – 2.5

Flowrate (l/h)

0.04 – 2.5

Residence time (ms)

14.4 – 720

Residence time (ms)

27 – 1350

Inner volume (µl)

8

Inner volume (µl)

15

Max Viscosity (mPas)

10000

Max Viscosity (mPas)

10000

Leakage Class

< L0.001

Leakage Class

< L0.001

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SLIT INTERDIGITAL MICROMIXER SIMM GROUP CLASS SIMM-V2, HPIMM, SIMHEX, SSIMM

56 SIMHEX

SSIMM

03

Slit Interdigital Mixer Heat Exchanger (SIMHEX)

Principle

Standard Slit Interdigital Micromixer (SSIMM) 

Principle

This micromixer was optimized considering a heat exchange function within the mixer, using a graphite sealing for tightening the two parts of the housing. As a consequence, the limits of pressure and temperature during operation are limited but conveniently provide the possibility of heating or cooling the device. The mixer also comprises expansionfree outlet channel geometry, i.e. renounces on jet mixing, but relies on multi-lamination and geometric focusing only.

Technical Data

This micromixer is the classic one amongst all IMM chemical micro processing products. It combines the regular flow pattern created by multi-lamination with geometric focussing and subsequent volume expansion, which speeds up liquid mixing of the multi-lamellae and leads to jet mixing. Due to the volume expansion the mixer contains an inner volume of 40 µl and is only offered with non-stainless soft tube connectors.

Technical Data

Order number

SIMHEX

Order number

SSIMM

Mixing principles

Multi-lamination

Mixing principles

Multi-lamination

Size (L x B x H)

25 x 25 x 20

Size (L x B x H)

19 x 30 x 16.5

Connectors (Inlet/Outlet)

1/16˝ / 1/16˝ HPLC

Connectors (Inlet/Outlet)

1/16˝ / 1/16˝ soft tube

Standard mixing channels (µm)

40 x 300

Standard mixing channels (µm)

45 x 200

Standard material

Body: 1.4571 Inlay: 1.4401

Standard material

Body: 1.4571 Inlay: 1.4435

Options

Other materials like Hastelloy, Monell or Titan on request; incl. heat exchanger function

Options

Other materials like Hastelloy, Monell or Titan on request

Operating Conditions

Operating Conditions

Temperature (°C)

-100 – 500

Temperature (°C)

-20 – +100

Pressure stability (bar)

50

Pressure stability (bar)

3

Flowrate (l/h)

0.04 – 2.0

Flowrate (l/h)

0.04 – 1.5

Residence time (ms)

18 – 900

Residence time (ms)

72 – 3600

Inner volume (µl)

10

Inner volume (µl)

40

Max Viscosity (mPas)

10000

Max Viscosity (mPas)

10000

Leakage Class

< L0.001

Leakage Class

< L0.001

57 Slit mixer inlays SMI (for SIMM-V2 and SSIMM)

SIMHEX inlays SMHXI

High pressure mixer inlays HPMI

Laser ablation Inlay for SIMM-V2 and  SSIMM 

Laser-cut Inlay for SIMHEX 

Laser-cut Inlay for HPIMM 

This inlay fits the standard mixer as well as the version 2.

This inlay fits the slit interdigital mixer heat exchange exclusively.

This inlay fits the high-pressure slit mixer exclusively.

For both versions the inlays have a size of 11.0 mm x 7.5 mm and ~ 3.6 mm thickness with different possible channel sizes and depths.

The size of SMHXI inlays: 20 mm x 6 mm

The size of HPMI inlays: 8.0 mm in diameter and 250 µm in thickness

The following inlays are available: • Laser-ablation (channel width 45 µm, 200 µm channel depth) made of stainless steel (SS 316L) as standard but other materials like Hastelloy etc. or other channel dimensions on request, order number SMI-Lasab45200 • LIGA technology (channel width 25 µm or 40 µm) made from silver or nickel on copper with 300 µm channel depth, order numbers SMI-Ni25, SMI-Ni40, SMI-Ag25 or SMI-Ag40 • ASE (thermally oxidised silicon, channel width 30 µm or 50 µm) with 100 µm channel depth, order numbers SMI-Si30 or SMI-Si50. As these inlays are only 0.6 mm thick, extra bases of 3.0 mm thickness are needed

The following inlays are available: • Laser-cutted inlays (channel width 45 µm, 250 µm channel depth) made of stainless steel (SS 316L) as standard but other materials like Hastelloy etc. or other channel dimensions on request, order number SMHXI-45250

The following inlays are available: • Laser-cutted inlays (channel width 45 µm, 250 µm channel depth) made of stainless steel (SS 316L) as standard but other materials like Hastelloy etc. or other channel dimensions on request, order number HPMILas45250

     S      T      N      E      N      O      P      M      O      C

03

LIQUID/LIQUID MICROMIXER

58

LLMR-MIX

03

Liquid/Liquid Microreactor with internal Mixer – LLMR-MIX 

Principle The Liquid/Liquid Microreactor is mainly designed for highly exothermic reactions and can also be applied for contacting two immiscible liquids and performing a reaction thereby. It comprises two microstructured plates with integrated micro mixer and micro heat exchanger. Insofar, it is particularly designed for reactions that benefit from excellent heat transfer as well as fast mass transfer. The heat transfer is provided by specific surfaces of 2 3 10,000 m  /m in micro channels of a width of 200 µm at an aspect ratio of 6, whilst the fast mass transfer derives from the meanwhile incorporated interdigital micromixer, known from the SIMM series. The LLMR-MIX can be offered of different materials on request besides the standard stainless steel. Flow rates

Detail of the internal mixing section

from 50 ml/h up to 2 l/h are feasible, with residence times in the 0,3 – 18 s range. The reactor can be used up to 50 bar and 180°C (Viton, Chemraz gasket) or higher if graphite is applied. The laser-cut inlay of the LLMR-MIX 

59

LLMR-MIX-HC276 disassembled

LLMR-MIX explosion drawing  

     S      T      N      E      N      O      P      M      O      C LLMR-MIX made of Hastelloy

Technical Data

LLMR-SY; a reactor with internal arrangement of 4 LLMR-   MIX including delay loop 

Operating Conditions

Name

Liquid/Liquid Microreactor

Temperature (°C)

-20 to + 300

Order number

LLMR-Mix

Pressure stability (bar)

50

Mixing principles

Multi-lamination

Flowrate (l/h)

0.05 – 2

Size (L x B x H)

45 x 120 x 26

Residence time (s)

0.3 – 18

Connectors (Inlet/Outlet)

1/16˝ / 1/16˝ for chemicals 1/4˝ / 1/4˝ for cooling fluid

Max Viscosity (mPas)

1000

Leakage Class Standard mixing channels (µm)

45 x 200

< L0.01

Standard cooling channels (µm)

200 x 1200

Standard material

Housing, reaction and cooling plate: 1.4571 or 1.4539 Inlay: 1.4404

Options

Other materials like Hastelloy, Monell, Titan or plastics on request

03

SUPERFOCUS INTERDIGITAL MICROMIXER

60

SFIMM-V2

03

SuperFocus microstructured mixer SFIMM-V2-300

Central plate of the SFIMM-V2-300 

Principle Focusing mixers perform a multi-laminating step and geometrically focus the streams (in a way similar to hydrodynamic focusing) to thin the lamellae and then mix by diffusion. Physically speaking, this means having a nozzle feed array, a triangular-type focusing chamber and a thin mixing channel. The SuperFocus Mixer Version 2 (SFIMMV2) bases upon the simulation, design and characterisation of the former version SFIMM. Development target was to achieve even higher throughputs, to have a robust steel design, e.g. for high-pressure operation and to use a still higher focusing ratio, e.g. to reduce the sensitivity towards blockage. The SuperFocus mixer thus combines both high throughput, which is e.g. characteristic of the StarLam series and uniform flow patterns, which is e.g. characteristic for the SIMM components. Compared to the predecessor design more nozzles enable fluid feed. The nozzle width was enlarged, thus being less particle sensitive, albeit the final focused lamellae width of about 4 µm was kept, i.e. the focusing ratio was increased from 40 formerly to now 178 (and can be set higher on demand). To arrange as many as 138 nozzles, a large circular arc was chosen for the feed array. The mixing channel width and length compares to the former design so that the semianalytical and experimental reaction type based findings on the mixing time can be largely transferred to the new design. Although steel is employed as construction material, an optional inspection window may allow the monitoring of the flow patterns and of the mixing course. For the SuperFocus SFIMM-V2 throughput of about 350 l/h at a pressure loss of 3.5 bar was determined for watery systems. The formation of flow patterns is very uniform, i.e. a multi-lamellae flow is found all over the focusing chamber until the mixing channel is reached. The known deviations from ideal given for any multi-lamellae flow are found as well, e.g. that lamellae are thicker at the wall (boundary) than in the interior of the flow. In particular this deviation should be less here compared to other systems, as the ratio of outer to inner lamellae is 136:2.

Disassembled SFIMM-V2-300 

The mixing time achievable is 4 ms according to calculation and experiments made with the former design, albeit excluding the time needed for flowing through the focusing chamber. The latter is dependent on the volume flow. Specialty designs with notably reduced focusing time are possible. The same holds for integrated mixing-heating element configurations, allowing one to perform fast temperature switches for starting and ending reactions in a very short, defined time frame, as e.g. done in quench-flow analysis.

61

Multi-lamellae flow in the SuperFocus microstructured mixer SFIMM-V2-300 

Technical Data Name

SuperFocus Interdigital Micromixer Version 2 -300

Order number

SFIMM-V2-300

Mixing principles

Multi-lamination

Size (L x B x H)

140 x 140 x 40

Connectors (Inlet/Outlet)

1/4˝ / 1/4˝

Standard mixing channels (µm)

500 µm x 5 mm

Number of feeding channels

138

Width of feeding channel

260

Focusing ratio

178

Standard material

1.4435

Options

Other materials like Hastelloy, Monell or Titan on request; heat exchanger function is possible

The SFIMM is meanwhile also pro-  duced as smaller device for about  one tenth of the original throughput, named SFIMM-V2-30 

03

Operating Conditions Temperature (°C)

-40 – 220

Pressure stability (bar)

100

Flowrate (l/h)

10 – 300

Max Viscosity (mPas)

10000

Leakage Class

< L0.001

     S      T      N      E      N      O      P      M      O      C

Mixing structure of SFIMM-V2-30 

SFIMM-V2-30 with straight outlet for  high viscosity emulsions 

IMPINGING-JET MICROMIXER

62

IJMM

03

Impinging-Jet Micromixer 

Principle Deliberately slow mixing is an issue when fast mixing would have deleterious effects on processing, e.g. by plugging the whole system. As a matter of fact, most organic processes are associated with more or less precipitation during the course of reactions. Particle generation is simply not possible in the vast majority of today’s micro devices. For this reason, a specialty mixer was developed that performs mixing in a ”wall-free” environment, i.e. by two pump-driven, falling jets merging into one in a Y-shaped configuration. It was shown that the smaller the jet diameter, the better the mixing quality. Intense knowledge on jet configuration as a function of flow rate and jet diameter has been documented, in addition to mixing quality judgement.

As a result, the nozzles of the jet mixer have tiny, only 350 µm wide nozzles. The mixer has been tested for inorganic reaction processing such as calcium carbonate precipitation and organic reaction that are associated by strong fouling. The aminolysis of acetyl chloride with n-triethylamine in THF leads to instantaneous heavy precipitation. This reaction hardly can be handled in any other micro device. It is an extreme representative of many other organic reactions that suffer more or less from fouling, e.g. like quaternizations.

3 different flow patterns:  • Y-type jet of IJMM (top)  • Fan-shaped jet (middle)  • Fanned-out jet (down) 

63 Fluid A

IJMM in a special funnel-like housing for particle production

Fluid B 

Geometric parameters determine the mixing performance, beside flow parameters 

Technical Data Name

Impinging-Jet Micromixer

Order number

IJMM

Mixing principles

Jet collision

Size (L x B x H)

10 x 35 x 10

Connectors (Inlet/Outlet)

1/8˝ / 1/8˝ Clamp screw

Standard boring-/nooz le diameter d (µm)

350, 500, 1000

Orientation angles (d)

45°, 60°, 90°

Standard material

1.4571

Options

Other materials like Hastelloy, Monell or Titan on request

03

Impinging-Jet micromixer Plant, IJMP, cf. plant section, including heat exchang-  ers, pumps, process control system

Operating Conditions Temperature (°C)

-40 – 220

Pressure stability (bar)

10

Flowrate (l/h)

0.5 – 3

Residence time (ms)

0

Inner volume (µl)

0

Max Viscosity (mPas)

100

Leakage Class

< L 0.001

     S      T      N      E      N      O      P      M      O      C

IJMM in adequate housing as used for  IJMP 

FA L L I N G F I L M M I C R O R E A C T O R

64

FFMR GROUP

03

Members of the extended Falling Film Microreactor family 

Principle The Falling Film Microreactor utilizes a multitude of thin falling films that move by gravity force for a typical residence time of seconds up to about one minute. Its unique properties are the good temperature control by an integrated heat exchanger and the specific interface of 20,000 m2 /m3. Such high mass and heat transfer were e.g. exploited when performing direct fluorination of toluene with elemental fluorine in the original version of IMM´s Falling Film Microreactor (FFMR-STANDARD). This so far uncontrollable and highly explosive reaction could be managed under safe

conditions and with control over the reaction mechanism and therewith selectivity. Due to the high raised interest for such a kind of device, starting from the FFMR-STANDARD in recent years the concept has faced several extensions and even more important has been brought from lab scale to pilot and production scale. The several types of Falling Film Microreactors including the new ones are introduced in the following.

65

Falling film principle in a multi-  channel architecture 

Thermographic monitoring: Initial wetting flow (FFMR-STANDARD) 

FFMR Standard

Reactor assembled

Reactor disassembled

Reaction plates  

Research Topics at IMM  IMM is exploring the potential of further structuring the straight reaction channels in the Falling Film Microreactor. So IMM realised recently a reaction plate in which each of the channels have been modified by incorporation of additional grooves in order to improve via recirculation flows the liquid side mass transport. First tests based on CO2 absorption in aqueous sodium hydroxide have proven that significant performance improvements can be achieved.

Technical Data

03 Operating Conditions

Name

Falling Film Microreactor (Standard)

Temperature (°C)

180 (option: 300)

Order number

FFMR-STANDARD

Pressure stability (bar)

10 (without Borofloat glass: 20)

Size (L x B x H)

120 x 76 x 40

Flowrate (l/h)

Connectors (Inlet/Outlet)

all 1/4˝

0.05 for channel geometry 300 µm 0.6 for channel geometry 600 µm 1.5 for channel geometry 1200 µm

Material

1.4571 for housing and reaction plate Copper for cooling plate Borofloat glass for inspection

Residence time (s)

0.8 – 20

Liquid film thickness (µm)

25 – 100

300 x 100 (64 channels) 600 x 200 (32 channels) 1200 x 400 (16 channels)

Interfacial area (m 2 /m3)

up to 20000

Leakage Class

L0.01

Standard reaction channels (µm) Reaction channel length (cm)

7.6

Gas chamber height (mm)

5 3

volume of gas chamber (mm )

13336

Standard cooling channels (mm)

Width: 1.5 Depth: 0.5

Options

Other materials like Hastelloy, Monell or Titan on request

     S      T      N      E      N      O      P      M      O      C

66

FFMR GROUP

FFMR-LARGE & FFMR-CYLINDRICAL

03

Reaction plates for FFMR-STANDARD and -LARGE 

FFMR-STANDARD and -LARGE 

Starting from FFMR-STANDARD two new reactor types have been developed targeting at a tenfold increase of the structured surface area on the reaction plate. In the FFMR-LARGE therefore the length and the number of channels have been increased by a factor of 100.5. From the general design FFMR-LARGE is quite similar to FFMR-STANDARD. FFMR-CYLINDRICAL follows another approach. The reaction channels are now engraved on the outside of a metallic tube. The cylindrical shape allows a quite compact design in this case. The number of the reaction channels has been increased by a factor of 7.5, the length of the channels has been elongated a bit to get a tenfold increase of structured surface area. The FFMR-CYLINDRICAL is of special interest for photochemistry applications. FFMR-CYLINDRICAL

Technical Data Name

Falling Film Microreactor Large

Falling Film Microreactor Cylindrical

Order number

FFMR-LARGE

FFMR-CYLINDRICAL

Size (L x B x H)

320 x 156 x 40

80 x 130

Connectors

all 1/4´´

1/8´´ and 1/4´´ (welded tubes)

Material

1.4571 for housing and reaction/cooling plate Quartz glass for inspection

1.4571 DURAN® glass for inspection

Standard reaction channels (µm)

1200 x 400 (50 channels)

1200 x 400 (120 channels)

Reaction channel length (cm)

about 25

about 10

Gas chamber height (mm)

4,5

5

Volume of gas chamber (mm3)

90000

100000

Standard cooling channels (mm)

Width: 0.2 Depth: 0.4

Width: 1.2 Depth: 1.0

Options

Other materials on request

Other materials on request

Temperature (°C)

180

180

Pressure stability (bar)

10 (without glass: 20)

5

Flowrate (l/h)

investigated range 0.24 - 1.20

investigated range 0.24 - 1.20

Residence time (s)

calculated 23 - 8

calculated 16 - 6

Liquid film thickness (µm)

calculated 60 - 100

calculated 45 - 76

Interfacial area (m2 /m3)

about 9814 - 16780

about 13140 - 22470

Operating Conditions

67 Brazed Falling Film Microreactors (STACK-FFMR)

STACK-1x-FFMR-LAB

STACK-1x-FFMR-LARGE (open/closed) 

STACK-10x-FFMR-LARGE  

The reactor concept of FFMR-STANDARD and -LARGE has been transferred to a pure plate design to which brazing as joining technology can be applied. The STACK-1x-FFMR-LARGE thereby represents the equivalent to FFMR-LARGE and the basic functional element for following numbering-up. So STACK-10x-FFMRLARGE contains 10 functional elements. To round up the brazed reactor program also a new lab version has been developed (STACK-1x-FFMR-LAB). Compared to STACK-10x-FFMR-LARGE it should allow identical experimentation at a throughput of only 1/100 of the STACK-10x-FFMR-LARGE. Brazing technology opens the door for specifically adopted reactors for high pressure applications.

Outlook for even larger reactors:  test reaction plate  for FFMR-XXL

Technical Data Name / Order number

STACK-1x-FFMR-LAB

STACK-1x-FFMR-LARGE

STACK-10x-FFMR-LARGE

Size (L x B x H)

294 x 28 x 19

296 x 118 x 12

296 x 118 x 75

Connectors

all 1/8´´

all 3/8´´

all 3/8´´

Material

1.4571 + Ni screen printing braze

1.4571 + Ni screen printing braze

1.4571 + Ni screen printing braze

Standard reaction channels (µm)

1200 x 400 (50 channels)

1200 x 400 (50 channels)

1200 x 400 (50 channels)

Reaction channel length (cm)

about 25

about 25

about 25

Reaction channels number

5

50

500

Gas chamber height (mm)

4

4

4

Volume of gas chamber (mm3)

7300

73000

730000

Standard cooling channels (mm)

Width: 1.2 Depth: 0.4

Width: 1.2 Depth: 0.4

Width: 1.2 Depth: 0.4

Options

On request

On request

On request

Temperature (°C)

180

up to 800 @ 1 bar

up to 800 @ 1 bar

Pressure stability (bar)

10

up to 50 @ 25 °C

up to 50 @ 25 °C

Flowrate (l/h)

about 0.02 - 0.12

about 0.24 - 1.20

about 2.4 - 12.0

Residence time (s)

about 23 - 8

about 23 - 8

about 23 - 8

Liquid film thickness (µm)

about 60 - 100

about 60 - 100

about 60 - 100

Interfacial area (m2 /m3)

about 9814 - 16780

about 9814 - 16780

about 9814 - 16780

Operating Conditions

     S      T      N      E      N      O      P      M      O      C

03

GAS PHASE MICROREACTOR

68

GPMR

03

Gas Phase Microreactor 

Principle The Gas Phase Microreactor comprises a stack of several microstructured plates (generally 10 + 10 plates) that are arranged for counter-flow or co-current flow practice. Each plate consists of 34 parallel micro c hannels of 300 µm width and 200 µm depth. The plate stack is encompassed by two ® ceramic Macor plates, for thermal insulation to the environment and the two steel end caps. The GPMR is a modular system which can also be customized (e.g. one passage solely with electrical heating: No insulation plates, special designed end caps with integrated heat cartridges).

Intense studies on periodic reactions were made with this reactor by three well-known European research groups, concerning the oxidation of propane, the dehydration of isopropanol, and the selective oxidation of isoprene to citraconic anhydride.

The plates can be coated with catalyst, so that the assembled device can be operated as gas-phase reactor, either with or without internal heat transfer.

The device can also be used as a gasphase and/or liquid-phase micro heat exchanger.

On request, catalyst deposition in the micro channels can be offered as well. Most commonly, wash coating of different carriers, e.g. of various aluminas, and subsequent catalyst impregnation are applied. Coprecipitation and sol-gel techniques were applied as well for catalyst deposition.

Counter-flow principle 

69

Gas phase reactor installed in bench-scale plant 

Plate coated with catalyst 

Technical Data Name

Gas Phase Microreactor

Order number

GPMR

Size (L x B x H)

70 x 70 x 55

Connectors (Inlet/Outlet)

1/8˝

Standard material

1.4571 for housing and catalyst carrier Glass ceramics MACOR for insulation layer

Number of catalayst plates

20

Size of catalyst plate (mm)

40 x 40

Channel geometry of the catalyst plates (µm)

300 x 200

Options

GPMR is also usable as a single heat exchanger; end caps for heating cartridges

GPMR integrated into a plant, here  as simple heat exchanger (COMH) for  education purpose 

Operating Conditions Temperature (°C)

500

Pressure stability (bar)

3

Flowrate (l/h) liquid/gas

1 – 7 / 1 – 600

Leakage Class

L0.1 2

3

Heat transfer area (m  /m )

18000 2

Total inner surface per layer (mm )

580

2

3

Specific inner surface per layer (m  /m ) 3

     S      T      N      E      N      O      P      M      O C

2900

Active inner volume per layer (mm )

32

Operation mode

Counter- or co-current flow

03

70

GAS PHASE MICROREACTOR WITH MIXER A N D I N T E R N A L H E AT I N G / C O O L I N G GPMR-MIX

03

Gas Phase Microreactor with Mixer and Internal Heating/  Cooling 

Top housing plate of reactor with mixer and reactor stack 

Principle The Gas Phase Microreactor with Mixer and Internal Heating/Cooling GPMR-MIX contains two recesses, each filled with one stack of microstructured platelets, which are connected via a conduit. Both stacks are connected to welded tubes, serving for feed and fluid withdrawal. The first stack comprises two types of mirror-imaged platelets with parallel feeding channels which are alternately arranged so that a multi-lamination flow configuration is created for gas mixing. In the conduit attached, forming a flow-through chamber, mixing is completed within short time due to the virtue of decreasing the diffusion path. Hence the mixed reactant gas volume (before reaction) is kept as small as possible. As a result, investigations in the explosive regime are safely amenable, as demonstrated by research with this and similar tools. The second stack comprises platelets with parallel channels of small depth so that very good heat transfer is provided. By this means, hot-spots are reduced and near-isothermal operation can be achieved. The platelet construction material itself may act as catalyst or, more preferably, the channels may be coated with a catalyst layer, e.g.

wet chemically using the wash-coat route or by means of thin-film deposition. A small total mass of the construction material, hence a compact arrangement of the functional units, and internal large-power heat supply guarantee fast heating up, typically in the range of a few minutes (ca. 100 K/min), even when approaching rela-tively large temperatures, e.g. up to 600°C. Internal cooling typically of similar time scale is provided by convection flow of a gas stream at high flow rate in a channel which surrounds the functional units. The mixer-catalyst zone reactor has been extensively studied for its use for ethylene oxide synthesis. Among other results of the parametric study, safe operation in the ex regime (3 vol.-% ethylene, 50 vol.-% oxygen, balance nitrogen; 5 bar; 4 l/h; 277°C), high space-time yields (up to 0.78 tons -1 -3 h m ), a maximum selectivity of 69% (6 vol.-% ethylene, 30 vol.-% oxygen, balance nitrogen; 5 bar; 0.124 s; 5 l/h; 290°C), not far from the industrial benchmark, and higher conversions at comparable selectivity compared to fixed-bed technology (20 vol.-% ethylene, 80 vol.-% oxygen; 0.3 MPa; 3.17 l/h; 230/250°C) were demonstrated.

Schematic of the GPMR-Mix device  and details of the functional principle 

71

Individual parts of GMPR-Mix

Mixer and reaction platelet

Laser-cut mixer platelets  

Technical Data Name

Gas Phase Microreactor with Mixer and Internal Heating

Order number

GPMR-MIX

Size (L x B x H)

40 x 40 x 30

Connectors (Inlet/Outlet)

1/4˝

Standard material

Inconell 600 (2.4816) for housing and top plate 1.4571 for mixing and catalyst plates

Number of mixing plates

10

Size of mixing plates (mm)

7.5 x 7.5

Channel geometry of mixing plates (µm)

180 – 490 x ~ 100

Number of catalayst plates

10

Size of catalyst plate (mm)

9.5 x 9.5

Channel geometry of the catalyst plates (µm)

460 x 125

03

Operating Conditions Temperature (°C)

600

Pressure stability (bar)

50

Flowrate (l/h)

5

Residence time (s)

0.025 – 2

Leakage Class

< L0.1 2

3

Specific surface area (m  /m )

12700 2

Total inner surface per reaction layer (mm ) 2

54 3

Specific inner surface per reaction layer (m  /m ) 3

Active inner volume per layer (mm )

     S      T      N      E      N      O      P      M      O      C

3840 2.5

C AT A LY S T M I C R O B U R N E R R E A C T O R

72

CMBR

03

Catalyst Micro Burner Reactor 

Principle The Catalyst Micro Burner Reactor is a testing reactor composed of a housing which can take in a stack of up to 16 microstructured plates. The plates are easily exchangeable and the assembly of the reactor is simple.

with different catalysts, however, it may be as well applied as a testing reactor for all kind of heterogeneous gas phase reactions at flow-rates exceeding the range of small-scale laboratory devices.

On demand, the reactor plates can be coated with various carrier/catalyst systems. The CMBR was designed for testing the catalysed burning of fuels

Heating of the reactor is realised by heating cartridges with temperature determination feasible at two positions inside the reactor.

The Catalyst Micro Burner Reactor is designed for a power generation in the range of several hundreds of Watts by burning various fuels. Full conversion of 32 g/h methanol was achieved with a conventional Pt-catalyst at 130°C reaction temperature. No other products than carbon dioxide and water were found above the detection limit. Thus absence of bypass effects could be proven.

73

Single parts of the Catalyst Micro Burner Reactor 

Technical Data Name

Catalyst Micro Burner Reactor

Order number

CMBR

Size (L x B x H)

160 x 120 x 50

Connectors (Inlet/Outlet)

1/4˝

Standard material

1.4571

Number of catalayst plates

1 – 16

Size of catalyst plate (mm)

50 x 50

Channel geometry of the catalyst plates (µm)

600 x 400

Micro channel surface area per platelet (mm 2)

588

Options

Other materials on request

Operating Conditions Temperature (°C)

550

Pressure stability (bar)

5

Flowrate (l/h)

10 – 150

Residence time (ms)

0.10 – 1

Leakage Class

< L0.1

     S      T      N      E      N      O      P      M      O      C

03

CATALYST TESTING MICROREACTOR

74

CTMR

03

Catalyst Testing Microreactor with end caps for parallel operation

Principle The Catalyst Testing Microreactor consists of a housing comprising twenty micro structured plates positioned pairwise face to face resulting in ten levels of parallel microchannels. On demand, the micro structured plates can be coated with various carrier/catalyst systems. They are easily exchangeable using an included mounting tool and relatively inexpensive due to mass fabrication by wet-chemical etching. By simple exchange of the end caps a decision can be made whether to operate the microreactor in serial or in parallel mode.

Parallel operation (10 in, 10 out):

Even testing ten different catalysts using ten different gases (at similar pressure) can be applied by assembling the reactor with two end caps for parallel operation. 10 levels with different catalysts and/  or different gases. Screening or numbering-up of catalysts. Serial operation (1 in, 1 out):

Using a diffuser-type end cap, the microstructured plates are fed simultaneously by the one common inlet stream. The sub-streams leave then through the ten separate outlets that can be analyzed accordingly.

Using two other end caps similar in shape, the one inlet stream flows serially in a zigzag manner from one plate to the other, being turned around and guided to the next level and so on, finally resulting in a path of ten times length compared to the single plate length, respectively ten times the residence time.

10 levels with different catalysts but same feed gas.

Up to 10 plates with identical catalyst may be installed.

Screening of catalysts.

Variation of the reactor length.

Parallel operation (1 in, 10 out):

Stack of cartridges with coated micro-  structured plates 

Two end caps for parallel operation

75

Special version for 800°C and 20 bar  operation

Standard version disassembled

Alternative heating option with one  heat jacket instead of 10 heat cartridges 

Technical Data Name

Catalyst Testing Microreactor

Order number

CTMR

Size (L x B x H)

100 x 100 x 108

Connectors (Inlet/Outlet)

1/4˝ / 1/16˝ for parallel operation 1/8˝ / 1/8˝ for serial operation

Standard material

1.4841 for housing 1.4742 for catalyst plates

Number of catalayst plates

20

Size of catalyst plate (mm)

50 x 14

Options

Other materials on request

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Operating Conditions Temperature (°C)

800

Pressure stability (bar)

20 (100 bar at 400°C)

Standard flow velocity (m/s)

0.4 – 40

Residence time (ms)

0.025 – 2000

Leakage Class

< L0.1

03

Options Catalyst plates can be delivered with various channel geometries: Channel geometry (width µm x depth µm):

2900 x 300

Number of channels:

3

2000 x 300

4

1000 x 300

7

1000 x 100

7

750 x 300

9

750 x 100

9

500 x 300

12

500 x 100

12

L A S E R - W E L D E D M I C R O H E AT E X C H A N G E R

76

WT-SERIES

03

Laser-welded micro heat exchanger group class (WT-series), WT-404, WT-304, WT-204 (from left to right) 

Principle The WT-series was developed as a heat exchanger for liquid/liquid, gas/  liquid or gas/gas applications and can also serve for evaporation or condensation. They comprise a laser welded stack of arranged microstructured plates enabling a counter- or co-current flow scheme. Being assembled with conventional 1/4” or 3/8” tubes, easy integration into the existing tubing system of pilot- or small-scale production plants is possible.

The core elements are chemically etched microstructured plates, sealed by high-precision laser welding. These heat exchangers are normally designed for flow rates between 1 l/h up to 400 l/h; higher flow rates of up to 1000 l/h are possible at moderate pressure drops. The high efficiency and heat transfer coefficients of the micro channels are even more enhanced compared to conventional heat exchangers due to the low material thickness (low heat resistance) and high inner specific surface.

Single plates of the WT…04-series 

Additionally, the channels of plates can be coated with catalyst using the heat exchanger as reactor for heterogeneously catalysed reactions, typically gas-phase reactions, like e.g. steam reforming.

Single plates of the WT…08-series 

77 Technical Data Name

Laser-Welded Micro Heat Exchanger Series

Order number

WT 204

WT 304

WT 404

Size (L x B x H)

60 x 24 x 23

80 x 34 x 32

100 x 44 x 42

Connectors (Inlet/Outlet)

1/4˝ / 1/4˝

3/8˝ / 3/8˝

3/8˝ / 3/8˝

Material

316 Ti, others on request

Dimensions of heating channels (µm)

800 x 400, others on request

Operating Conditions Temperature (°C)

up to 1000 @ 1 bar

Pressure stability (bar) Flowrate (water, l/h)

5 @ 25 °C (higher upon request, max. 20 bar) 0.5 – 50

2.5 – 250

6 – 600

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Other examples of laser-welded micro heat exchangers 

Special type HxA

Special Heat Exchanger, also for   condensing 

HCOMH 

B R A Z E D M I C R O H E AT E X C H A N G E R S HX-SERIES

78

03

Brazed micro heat exchanger group class (HX-series); HX-204, HX-304 (top  right), HX-404 (bottom right) 

Principle

Single plates of the HX-304-series (left: blank, right: coated with screen printing  paste) 

This novel HX-series was developed as a heat exchanger for liquid/liquid, gas/liquid or gas/gas applications at high pressure and temperature regimes. They comprise a brazed stack of aligned plates enabling a counter- or co-current flow scheme. The core elements are chemically etched microstructured plates, laminary joined applying brazing technology. These new heat exchangers are normally designed for flow rates between 1 l/h up to 400 l/h; higher flow rates of up to 1000 l/h are possible at moderate pressure drops. The high efficiency and heat transfer coefficients of the micro channels are even more enhanced compared to conventional heat exchangers due to the low material thickness (low heat resistance) and high inner specific surface.

79 Technical Data Name

Brazed Micro Heat Exchanger Series

Order number

HX 204

HX 304

HX 404

Size (L x B x H)

ca. 100 x 60 x 20

ca. 150 x 80 x 25

ca. 200 x 120 x 40

Connectors (Inlet/Outlet)

1/4˝ / 1/4˝

3/8˝ / 3/8˝

1/2´´ / 1/2´´

Material

316 Ti, others on request

Dimensions of heating channels (µm)

1000 x 600, others on request

Operating Conditions Temperature (°C)

up to 800 @ 1 bar

Pressure stability (bar) Flowrate (water, l/h)

up to 500 @ 25 °C 0.5 – 50

2.5 – 250

10 – 1000

Brazed (high pressure) Microreactors

At IMM the microstructured reactor  plates are coated with the brazing  paste by using the screen printing  machine Type THIEME 1010 E.

High Pressure Microreactor with two temperature zones  (Type HPMR-2TZ-V2-90ml)) 

Section view of two brazed plates  aligned face to face 

Complex feed structures are feasible:  The picture shows the feeding struc-  ture for a SuperFocus like micromixer  with nozzle like outlets for an inner  liquid phase surrounded from top and  bottom from chains of rectangular  feed structures for the outer liquid  phase.

Research Topics at IMM  Brazing opens the possibility of interconnecting large-area reactor structures monolithically. Thereby large interior volumes are possible with high pressure strength at the same time. Further the brazing technique makes a multiplicity of new reactor geometries accessible. IMM extended strongly the application of the brazing technique as sealing technology for microreactors of different functionality. Besides the HX-series the technology has e.g. also been applied for realising the prototype of a high pressure microreactor with two temperature zones with a reactor interior volume on the reaction side of 90 ml (HPMR-2TZ-V2-90ml), which is tested for operation at 120 bar @ 250 °C.

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03

T U B E H E AT T R A N S F E R M I C R O D E V I C E

80

THTMD

03

Tube Heat Transfer Micro Device 

Principle The Tubular Heat Transfer Micro Device is a microstructured heat exchanger, designed for electrical heating of gases and liquids. The optimized size of this device allows a very fast heating up as well as fast changes of temperatures. Being offered in two sizes, the maximum power rate to be transferred can be up to 800 W with a thermal efficiency > 90% (depending on operation conditions). Several options can be offered: • THTMD solely • THTMD plus suitable heat cartridge (if suitable electronic control unit is at hand) • Full package, comprising THTMD plus heat cartridge, two thermocouples and electronic control unit

In the latter case, the temperature of the heating process is basically controlled by a thermocouple in the THTMD-outlet as well as an additional thermocouple to avoid overheating is integrated within the heating cartridge itself. Operation conditions are tested for maximum 300°C @ 1 bar or 45 bar @ 25°C.

Technical detail of heat exchanger  structure 

THTMD in parts before laser-welding 

81

Explosion drawing of THTMD

Heat control system for THTMD  

Technical Data Name

Tube Heat Transfer Micro Device

Order number

THTMD

Size (L x B x H)

120 x 100 x 15

Connectors (Inlet/Outlet)

1/4˝ / 1/4˝

Material

1.4571

Number of heating channels

60

Width of heating channels (µm)

400

Options

Other materials like Hastelloy, Monell or Titan on request

Operating Conditions Temperature (°C)

up to 500

Pressure stability (bar)

45

Flowrate (l/h) liquid

1.0 – 20.0

Power rate (W)

800

Thermal efficieny

> 90%

Leakage Class

L0.1

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03

L A B O R AT O R Y E VA P O R AT O R

82

03

Temperature control unit with integrated mass flow controller (upper box) and with integrated LV1 (lower box), front view  (left) and backside view (right) 

Principle The Evaporator System is a nearly pulsation-free continuous evaporator without the supply of carrier gas. It comprises a pair of microstructured plates together with a control system for the liquid flow as well as the electrical heating and its temperatures to ensure the continuous use. Rapid preheating, evaporation and over-heating are realized in one single device.

Two electrical heating cartridges supply the heat to the corresponding microstructured plates with large specific surfaces for excellent heat transfer. Up to 100 g/h water (without carrier gas) can be evaporated. A maximum temperature of 350°C for the vapour or up to 6 bar system pressure are feasible. LV1 – Laboratory evaporator for 100 g/h

83

LV1 – with open heating housing

LV1 – disassembled  

Technical Data Name

Evaporator System

Order number

LV1

Size (L x B x H)

300 x 300 x 360

Connectors (Inlet/Outlet)

1/8˝ / 1/8˝

Material

1.4301

Operating Conditions Temperature (°C)

400

Pressure stability (bar)

6

Temperature (°C) of Vapor

up to 350

Flowrate (g/h)

10.0 – 100.0

Power rate (W)

400

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03

84

GENERAL TERMS AND CONDITIONS OF DELIVERY AND SALE

1.

04

General Provisions

1.1 The terms and conditions set forth herein apply to deliveries and sales  to entrepreneurs, public legal persons and public special funds according to § 310 section 1 BGB (German Civil Code) (“Purchaser”) exclusively. 1.2 These terms and conditions apply to all our agreements and quotations, even to prospective agreements and quotations, and apply exclusively. 1.3 Purchaser’s conditions which are contradictory to or diverging from our  terms and conditions do not apply unless their validity is expressly agreed in written form. 1.4 These terms and conditions also apply in case we supply even though con tradiction or divergence of Purchaser’s conditions from our terms and conditions is known to us. 1.5 All agreements between us and Purchaser for the purpose of performance of the contract at hand require written form. This also applies to the waiver of the written form itself.

2.

Offers and Prices

2.1 Our offers are not binding until our written order confirmation is submitted. Oral offers are not valid unless a written confirmation is submitted.

3.8 Meeting respites of delivery requires timely receipt of all documents as well as required permissions and clearances and particularly of plans to be delivered by Purchaser, as well as compliance with agreed conditions of payment and other obligations by Purchaser. If these requirement are not timely fulfilled, respite of delivery will be adequately prolonged, unless we are responsible for the delay. 3.9 Delivery time will be extended adequately in case of force majeure, strike, lockout,breakdown,delayofexternal suppliersandotherunexpectedcircumstances. In such cases we reserve the right to withdraw from the contract  taking into account Purchaser’s interests. 3.10 If Purchaser defaults in payment in the context of other present contractual relationships between Purchaser and us, we are entitled to detain delivery under this contract for the duration of default of payment, prior notice to Purchaser provided. This shall not apply in case of minor outstanding payment. 3.11 In case of application to open insolvency proceedings as well as of affidavit of means according to § 807 ZPO (German Code of Civil Procedure) we are entitled to detain delivery until consideration has been executed or until Purchaser furnishes appropriate security. Furthermore, we are en  titled to claim full payment and – after futile expiration of a reasonable additional respite – to withdraw from the contract unless Purchaser furnishes adequate security on our demand.

4.

Payment Terms

2.2 Our prices are effective “ex factory” plus value added tax and costs of delivery and packaging.

4.1 Invoices are payable net within 30 days as of invoice date.

2.3 Unless a fixed priceagreement is reached,we reserve the right to adequately adjust the price due to changed costs for wages, material and distribution of deliveries, which are carried out three months after conclusion of the contract or later on.

4.2 Unless otherwise agreed, ordering amounts of more than 10.000,-- EURO will be invoiced in two rates of 50% of the order value each. If so and unless otherwise agreed, delivery will not be performed until receipt of the first rate. The second rate is due after delivery.

3.

4.3 Bills of exchange and cheques are only accepted on explicit agreement and only on account of performance and they shall not be deemed to constitute payment until honoured. In the event of such agreed submission of bills of exchange or cheques, payment shall only be deemed to have been made upon encashment, due payment provided.

Extent of Delivery and Performance

3.1 The order confirmation discloses the whole extent of the delivery and performance owed. 3.2 Purchaser bears the costs and risks of delivery. 3.3 In case we owe a separable performance, partial delivery is permitted for relevant reasons to a reasonable extent. We are entitled to invoice partial delivery separately. 3.4 Specifications as to time of delivery are not binding unless a binding time of delivery is expressly agreed. If we do not meet a binding time of delivery, Purchaser will be entitled to withdraw from the contract, if we do not deliver within an adequate additional respite granted by Purchaser. Upon our request Purchaser is obliged to declare within an adequate respite, whether he withdraws from the contract because of the delay of the delivery or demands delivery.

4.4 On default of payment Purchaser has to pay interest at 8 percentage points above the current base rate according to § 247 BGB (German Civil Code). We reserve the right to claim a higher damage as a result of default. 4.5 Purchaser will be entitled to set off with counterclaims only, if said claims are undisputed or legally confirmed. Purchaser is entitled to lay a lien on his payment only as far as the counterclaim is based on the same contractual relationship. In case of r easonable partial delivery Purchaser is not entitled to lay a lien on his payment for reasons of outstanding parts of delivery.

5. 3.5 If the Parties agree that our performance will not be initiated until down payment or advance payment has been made, delivery time will not begin unless the according amount has been credited to our business account subject to a separate agreement. 3.6 If we exceed time of delivery, Purchaser – in case Purchaser credibly shows,  that resulting from this he suffered damage – will be entitled to demand indemnification amounting to 0.5 % of the delivery value for each completed week of delay, but not exceeding a total of 5 % of the delivery value. 3.7 Damages claims of Purchaser resulting from delay of delivery as well as damages claims in place of delivery exceeding the limits set by foregoing no. 6 are excluded in all cases of delayed delivery, even after expiry of an additional respite of delivery. This shall not affect the cases where IMM’s liability is mandatory by law in cases of intent, gross negligence or damage  to life, body or health. The foregoing regulation does not stipulate a reversal of the burden of proof for Purchaser.

Retention of Title

5.1 We reserve the right of property in the delivery items until Purchaser completely satisfies our claims arising from the contract at hand. 5.2 As long as property is not transferred to Purchaser, Purchaser is obliged to  treat the delivery item with care. Particularly Purchaser is obliged to insure   the delivery item sufficiently according to its replacement value and at Purchaser‘s own expenses against damage caused by theft, fire and water. Claims arising from said insurances as well as everything possibly acquired as a substitute according to § 285 BGB (German Civil Code) are herewith assigned from Purchaser to us; we hereby accept assignment. Notwithstanding the assignment, Purchaser is authorised to assert and collect claims in his own name, by legal proceeding if necessary. Our entitlement   to collection of debts remains unaffected by Purchaser‘s authorisation. Necessary maintenance or inspections are to be performed by Purchaser at Purchaser‘s own expenses in due time.

85 of the delivery items in connection with special chemicals. If Purchaser or third parties carry out inappropriate maintenance or changes, no claims because of fault emerging from such inappropriate maintenance or changes will accrue.

5.3 In case of breach of contract, particularly of default of payment or breach of  these terms and conditions, we reserve the right to withdraw from the con tract at hand and to reclaim property. 5.4 In case of garnishment, requisition or other disposals or interventions of  third parties, Purchaser is obliged to notify us forthwith. Purchaser shall be liable for our detriment, if and to the extent to which third parties are not able to refund costs arising in or out of court for actions taken in accordance with § 771 ZPO (German Code of Civil Procedure). 5.5 Purchaser is entitled to resale delivery items under reserved property in regular course of business. Purchaser herewith assigns to us all claims against Purchaser‘s customers arising from said resale at the final amount of the invoice (incl. value added taxes). This assignment is valid irrespective of whether the delivery items under reserved property were resold without or after product processing. Even after cession Purchaser remains authorised to collect outstanding claims. This shall not influence our right   to collect the debt. However, we will not collect the debt as long as Purchaser fulfils his obligation of payment, Purchaser is not in default of payment, no application for opening insolvency proceedings is filed and payment has not been stopped. 5.6 If the delivery items under reserved property are worked, processed or modified by Purchaser, such working, processing and modification shall always be deemed to be performed on our behalf. In this case the remainder of Purchaser in the delivery item is continued in the worked, processed or modified item. Shall the delivery item under reserved property be processed or modified together with other objects not belonging to us, we acquire co-ownership in the resulting merchandise at an interest depending on the ratio of delivery items‘ objective value to the other objects‘ value which do not belong to us. Relevant value will be that at the time of working, processing or modification. The same shall apply in case of commingling, mixture or combination. Should the resulting merchandise consist of Purchaser‘s objects forming the main part, Purchaser herewith under takes to assign proportionate co-ownership to us according to our con tribution and keeps the ownership or co-ownership by us in safe custody. For securing our claims against the Purchaser Purchaser herewith assigns  to us all claims, which accrue to him from connection of the delivery items under reserved property with immovable property; we hereby accept assignment. 5.7 We hereby covenant to gradually release at Purchaser‘s demand the securities obtained by retention of title in so far as the property’s value exceeds the debts to be secured by more than 20 %.

6.

Transfer of Risk

6.1 If the delivery items are sent to Purchaser at Purchaser’s demand, Purchaser bears the risk of accidental destruction or deterioration of the delivery items from the time of dispatch and at the latest from the time the delivery items leave the works/storage. This applies irrespective of whether dispatch is initiated from place of performance and irrespective of who bears the costs of delivery. 6.2 If dispatch, service, execution of setting up or assembly, taking over for operation, or trial operation are delayed for reasons attributable to Purchaser or Purchaser is in default of acceptance for other reasons, risk will be transferred to Purchaser.

7.3 We do not accept liability for our product being apt for a special intention. All information, irrespective of being oral or written, relating to possible fields of application of our products, is served to the best of our knowledge. It is based on our experience and therefore is not guaranteed. Purchaser is responsible to inspect the suitability of our products for the intended fields of application. 7.4 We do not warrant freedom from third parties‘ rights in the delivery items. 7.5 Purchaser will examine the consignment immediately after receipt for damages. If any defect becomes apparent during such inspection or is later de tected, Purchaser has to give written notice thereof including description of the fault to us immediately, but not later than five (5) working days after delivery and discovery respectively. 7.6 If despite all applied diligence delivery items show a fault, which already existed at the time of transfer of risk, we will be entitled, subject to notice of defect in due time by Purchaser, to subsequent performance which may be carried out as elimination of defect or delivery of items free of defects, as our choice may be. Within an adequate respite we are entitled to subsequent performances done twice. Claims for recourse remain unaffected by foregoing regulations without restrictions. 7.7 In case subsequent delivery fails, Purchaser is entitled – claims for damages remain unaffected – to withdraw from the contract or demand price reduction. 7.8 Should complaints turn out to be unjustified and should we not have given reasons therefore, Purchaser has to reimburse any and all of our costs in connection with the putative subsequent performance which we could reasonably deem appropriate. 7.9 Claims of Purchaser because of expenditures for the purpose of subsequent performance, particularly expenses for delivery, infrastructure, wages and material, will be excluded, if additional expenses are caused by subsequent transfer of the delivery items to a place other than Recipient‘s site unless transfer corresponds to the delivery item‘s conventional use. 7.10 Claims for recourse of Purchaser against us only accrue insofar as Purchaser has not agreed with his customer on terms regarding claims for faulty delivery, which exceed the warranty, which is mandatory by law. Concerning the extent of the claims for recourse of Purchaser against us no. 9 shall apply mutatis mutandis. 7.11 Damages claims of Purchaser because of material defects or defects as  to the quality are excluded. This does not apply in case of fr audulent concealment of the defect, noncompliance of guarantee of condition, in case of harm of life, body, health or liberty nor in case of intended or grossly negligent violation of duty. The foregoing regulation does not stipulate a reversal of the burden of proof for Purchaser. Claims of Purchaser because of material defects or defects as to the quality exceeding or differing from  this clause VII. are excluded.

8. 7.

Other Damages Claims

Liability for Faulty Goods

7.1 Period of warranty shall expire twelve (12) months after time of delivery. 7.2 Claims because of fault are excluded in case of negligible deviation, devia  tion being customary in trade and technically unavoidable deviation from   the agreed condition, in case of negligible impairment of serviceability, in case of fair wear and tear and damages, which accrue after transfer of risk because of careless or faulty treatment, immoderate stress, use of unapt equipment or because of special exterior influences, which are not subject to the contract at hand. Claims because of fault are excluded in case of corrosion damage unless Purchaser pointed out the intended use

8.1 All other damages claims of Purchaser are excluded no matter what legal ground they are based on, particularly in case of violation of duty of the contractual relationship and of tort. 8.2 This shall not affect the cases where our liability is mandatory by law, like e.g. according to Produkthaftungsgesetz (German Code of Liability for Faulty Products), in case of intent, gross negligence, damage to life, body or health, and in case of breach of cardinal contractual obligations. The liability of IMM in case of breach of cardinal contractual obligations shall be limited to the foreseeable, typically occurring damages. This shall not apply in case of intent, gross negligence, and damage to life, body or health. The

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04

GENERAL TERMS AND CONDITIONS OF SALE

86 foregoing regulation does not stipulate a reversal of the burden of proof for Purchaser.

04

9.

Title and Copyright

9.1 We reserve all copyright and rights of ownership concerning all samples, illustrations, drawings, calculations or other documents and information given to Purchaser. 9.2 Purchaser is obliged to keep secret all samples, illustrations, drawings, calculations or other documents and information received. They shall not be made accessible to third parties without our explicit consent. 9.3 The above duty of secrecy shall survive performance of the contract at hand but shall lapse if and in so far as the information included in the en trusted samples, illustrations, drawings, calculations or other documents and information has become common knowledge. 9.4 Purchaser is not allowed to disassemble the delivery items, samples etc., and/or to analyse or to examine or to have analysed delivery items‘, samples‘ etc. composition, functioning, working or similar, or to manipulate delivered items, samples etc. in any other way.

10. Intellectual Property Rights 10.1 Purchaser warrants that production of items according to Purchaser‘s instructions does not infringe third parties‘ rights. 10.2 Should infringement of said rights be substantiated to us by a third par ty, we are entitled to stop any further activity being in opposition to said rights. If so, Purchaser will indemnify us from third parties‘ claims on first demand. 10.3 Purchaser‘s obligation of release from liability comprises any expenditure we necessarily incur in the context of third parties‘ claims. 10.4 Our claims for damages remain unaffected. 10.5 Statute of limitation concerning said claims expires ten (10) years as of conclusion of the respective contract.

11. Applicable Law 11.1 The Laws of the Federal Republic of Germany shall apply exclusively to this contract.

12. Place of Performance – Place of Jurisdiction 12.1 Place of performance for all contractual duties shall be our place of business. 12.2 Any action concerning disputes arising from this contractual relationship shall be taken at the court, which is competent for our place of business.

13. Severability Clause Should one or several provisions of the contract be or become completely or partly void, regardless of the reasons thereof, or contain a loophole, validity of the other provisions shall not be affected thereby. Mainz, April 2009, Institut für Mikrotechnik Mainz GmbH

REFERENCES

87 Hessel, V., Renken, A., Schouten, J.C., Yoshida, J.-I.:

„Micro Process Engineering - A Comprehensive  Handbook” , three-volume edition, Wiley-VCH, Weinheim, 2009. Hessel, V., Löb, P., Löwe, H.; „Volume 3, Part III, 9

“Industrial Microreactor Process Development  up to Production“ in: „Micro Process Engineering  – A Comprehensive Handbook“ (eds.: Hessel, V., Renken, A., Schouten, J. C., Yoshida, J.-I.), 2009, pp. 185 – 247. Kralisch, D., Krtschil, U., Roberge, D. M., Hessel, V., Schmalz, D.; „ Volume 3, Part V, 13 The Economic  Potential of Microreaction Technology“ in: „Micro 

Jähnisch, K., Hessel, V., Löwe, H., Baerns, M.; “Chemistry in Microstructured Reactors” , Angew. Chem. Int. Ed. 43, 4 (2004) 406-446. Kolb, G., Hessel, V.; “Microstructured reactors for  gas phase reactions: a review”, Chem. Eng. J. 98, 1-2 (2004) 1-38. Pennemann, H., Watts, P., Haswell, S., Hessel, V., Löwe, H.; “Benchmarking of microreactor applications”, Org. Proc. Res. Dev. 8, 3 (2004) 422-439. Pennemann, P., Hessel, V., Löwe, H.; “Chemical 

micro process technology – from laboratory scale  to production”, Chem. Eng. Sci. 59, 22-23 (2005)

Process Engineering - A Comprehensive Handbook“ (eds.: Hessel, V., Renken, A., Schouten, J. C.,

4789- 4794.

Yoshida, J.-I.), 2009, pp. 281 – 296.

a review on passive and active mixing priciples”,

Hessel, V., Löwe, H., Schönfeld, F.; “Micro mixers – 

Renken, A., Hessel, V. Löb, P., Miszczuk, R., Uerdingen, M.; “Ionic liquid synthesis in a micro  structured reactor for process intensification” , Chem. Eng. Proc. (2007) Chem. Eng. Process 46, 9 (2007) 840-845. Löb, P., Hessel, V., Hensel, A., Simoncelli, A.;

„Micromixer based liquid/liquid-dispersion in the  context of consumer good production with focus  on surfactant vesicle formation“ , Chimica oggi – Chemistry Today 25, 3 (2007) 26-29. Men, Y., Hessel, V., Löb, P., Löwe, H., Werner, B., Baier, T.; „Determination of the segregation index 

to sense the mixing quality of scale-up concepts  for pilot- and production-scale micro structured  mixers“ , Trans. IChemE, Part A., Chem. Eng. Res. Dev. 85, A5 (2006) 1-8.

Löb, P., Hessel, V., Simoncelli, A.; “Microreactor  Applications in the Consumer Goods Industry” in

Chem. Eng. Sci. 60 (2005) 2479-2501.

„Micro Process Engineering - A Comprehensive  Handbook, Volume 2: Devices, Reactions and  Applications“ , V. Hessel, A. Renken, J.C. Schouten,

inations and brominations of organic compounds  in micro structured reactors”, J. Fluorine Chem.

Hardt, S., Schilder, B., Tiemann, D., Kolb, G., Hessel, V., Stephan, P.; “Analysis of flow patterns emerging  during evaporation in parallel microchannels” , J. Intern. Heat & Mass Transfer 50, 1-2 (2007) 226-239.

125, 11 (2004) 1677-1694.

Löb, P., Pennemann, H., Hessel, V., Men, Y.; „Impact 

Al-Rawashdeh, M., Hessel, V., Löb, P., Mevissen, K., Schönfeld, S.; “Pseudo 3-D simulation of a falling 

of fluid path geometry and operating parameters on  l/l-dispersion in interdigital micromixers“ , Chemical

J.-I. Yoshida (Eds.), WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2009. (Chapter 22 pp. 363-401). Hessel, V., Kolb, G., Brandner, J. J.; „Microfabri-

cation for Energy Generating Devices and  Fuel Processors“ in: „Microfabricated Power  Generation Devices“ (eds.: Mitsos, A.; Barton, P. I.), Wiley-VCH, Weinheim, 2009, pp. 7 -37. Hessel, V., Löb, P., Löwe, H.; „Industrial Micro-

reactor Process Development up to Production“  in: “Microreactors in Organic Chemistry and  Catalysis” (ed. Wirth, T.), Wiley-VCH, Weinheim, 2008, pp. 211-275. Schenk, R., Hessel, V., Jongen, N., Buscaglia, V., Guillemet-Fritsch, S., Jones, A. G.; „Nanopowders  produced using microreactors“ , Encyclopedia of NANOSCIENCE and NANOTECHNOLOGY, Vol. 7, 2003, pp. 287-296. Hessel, V., Löwe, H., Müller, A., Kolb, G.; Chemical 

Micro Process Engineering – Processing and  Plants, Wiley-VCH, Weinheim (2005). Hessel, V., Hardt, S., Löwe, H.; Chemical Micro 

Process Engineering – Fundamentals, Modelling  and Reactions, Wiley-VCH, Weinheim (2004). Ehrfeld, W., Hessel, V., Haverkamp, V.; “Microreactors”, in: Ullmann’s Encyclopedia of Industrial  Chemistry, Wiley-VCH, Weinheim (1999). V. Hessel, C. Serra, H. Löwe, G.Hadziioannou; “Poly-

merisationen in mikro-strukturierten Reaktoren: Ein  Überblick“, Chem. Ing. Tech. 77, 11 (2005) 39-59. Hessel, V., Angeli, P., Gavriilidis, A., Löwe, H.;

“Gas/liquid and gas/liquid/solid microstructured  reactors – contacting principles and applications”, Ind. Eng. Chem. Res. 44, 25 (2005) 9750-9769. Hessel, V., Löb, P., Löwe, H.; “Development of micro-

structured reactors to enable organic synthesis  rather than subduing chemistry” , Curr. Org. Chem. 9, 8 (2005) 765-787.

Löb, P., Löwe, H., Hessel, V.; “Fluorinations, chlor-

film microreactor based on realistic channel and  film profiles“ , Chem. Eng. Sci. 63, 21 (2008) 5149-

Engineering Science 61 (2006) 2959-2967.

5159.

Krtschil, U., Hessel, V., Kralisch, D., Kreisel, G., Küpper, M., Schenk, R.; „Cost analysis of a

V. Hessel, D. Kralisch, U. Krtschil; „Sustainability 

commercial manufacturing process of a fine  chemical using micro process engineering“ ,

through Green Processing – Novel Process Windows intensify Micro and Milli Process Technologies“ , Energy Environ. Sci. 1, 4 (2008) 467- 478. Hessel, V., Knobloch, C., Löwe, H., „Review on 

patents in microreactor and micro process  engineering“ , Rec. Pat. Chem. Eng. 1 (2008) 1-16. Pennemann, H., Hessel, V., Kolb, G., Löwe, H., Zapf, R.; „Partial oxidation of propane using a micro  structured reactor“ , Chem. Eng. J. 135, 1 (2008) S66-S73. Rosenfeld, C.; Serra, C.; Brochon, C.; Hessel, V.; Hadziioannou, G.; “Use of micromixers to control 

the molecular weight distribution in continuous  two-stage nitroxide-mediated copolymerizations” ,

Chimia 60, 9 (2006) 611-617. Zapf, R., Kolb, G., Pennemann, H., Hessel, V.;

„Basic study of the adhesion of several aluminabased washcoats deposited onto stainless steel  microchannels“ , Chem. Eng. Technol. 29, 12 (2006) 1509-1512. Hessel, V., Serra, C., Löwe, H., Hadziioannou, G.; „Polymerisationen in mikro strukturierten  Reaktoren: Ein Überblick“ , Chem. Ing. Tech. 77, 11 (2005) 39-59. Hessel, V., Löb, P., Löwe, H.; “Direct fluorination of 

aromatics with elemental fluorine in microstructured reactors”, Chimica oggi – Chemistry Today 5

Chem. Eng. J. 135, 1 (2008) S242-S246.

(2004) 10-15.

Kolb, G., Cominos, V., Hofmann, C., Pennemann, H.; Schürer, J., Tiemann, D., Wichert, M., Zapf, R., Hessel, V., Löwe, H.; „Integrated microstructured  fuel processors for fuel cell applications“ , Chem. Eng. Res. Des. 83, 6 (2008) 626-633.

Hessel, V., Hofmann, C., Löb, P., Löhndorf, J., Löwe, H., Ziogas, A.; “Organic Process Research & Development”, 9, 4 (2005) 479-489.

Men, Y., Kolb, G., Zapf, R., Tiemann, D., Wichert, M., Hessel, V., Löwe, H.; „A complete miniaturised 

Löb, P., Hessel, V., Klefenz, H., Löwe, H., Mazanek, K.; “Letters of Organic Chemistry”, 2, 8 (2005) 767779.

microstructured methanol fuel processor / fuel  cell system for low power applications“ , Int. J. Hydrogen Energy 33, 4 (2008) 1374-1382. Men, Y., Kolb, G., Zapf, R., Hessel, V., Löwe, H.; „Ethanol steam reforming in a microchannel reactor“, Trans. IChemE, Part B, Process Safety & Environmental Protection 85, B5 (2007) 1-6. Kolb, G., Schürer, J., Tiemann, D., Wichert, M., Zapf, R., Hessel, V., Löwe, H.; „Fuel Processing 

in Integrated Microstructured Heat-Exchanger  Reactors“ , J. Power Sources 171, 1 (2007) 198-204.

Pennemann, H., Hessel, V., Löwe, H.; “Chemical  Engineering Science”, 59, 22-23 (2004) 4789-4794.

Pennemann, H., Forster, S., Kinkel, J., Hessel, V., Löwe, H., Wu, L., “Org. Proc. Res. Dev.“, 9, 2 (2005) 188-192. Jähnisch, K., Dingerdissen, U.; “Chemical Engineering and Technology”, 28, 4 (2005) 426-427. Müller, A., Cominos, V., Horn, B., Ziogas, A., Jähnisch, K., Grosser, V., Hillmann, V., Jam, K. A., Bazzanella, A., Rinke, G., Kraut, M.; “Chemical  Engineering Journal”, 107, 1-3 (2005) 205-214.

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