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NL2003257C2 - Chemical transistor. - Google Patents

Chemical transistor. Download PDF

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Publication number
NL2003257C2
NL2003257C2 NL2003257A NL2003257A NL2003257C2 NL 2003257 C2 NL2003257 C2 NL 2003257C2 NL 2003257 A NL2003257 A NL 2003257A NL 2003257 A NL2003257 A NL 2003257A NL 2003257 C2 NL2003257 C2 NL 2003257C2
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Netherlands
Prior art keywords
energy
reactor
pulse
reaction
catalyst
Prior art date
Application number
NL2003257A
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Dutch (nl)
Inventor
Antonius Cornelis Petrus Maria Backx
Original Assignee
Insolutions B V
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Publication date
Application filed by Insolutions B V filed Critical Insolutions B V
Priority to NL2003257A priority Critical patent/NL2003257C2/en
Priority to PCT/NL2010/050467 priority patent/WO2011010917A1/en
Priority to EP10736848A priority patent/EP2456551A1/en
Application granted granted Critical
Publication of NL2003257C2 publication Critical patent/NL2003257C2/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093Microreactors, e.g. miniaturised or microfabricated reactors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00819Materials of construction
    • B01J2219/00835Comprising catalytically active material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00851Additional features
    • B01J2219/00853Employing electrode arrangements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781Aspects relating to microreactors
    • B01J2219/00925Irradiation
    • B01J2219/00927Particle radiation or gamma-radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0892Materials to be treated involving catalytically active material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894Processes carried out in the presence of a plasma
    • B01J2219/0896Cold plasma

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Description

Chemical transistor
Field of the invention
The invention relates to a process for the production of a compound and to a micro 5 reactor for performing such process.
Background of the invention
The petrochemical, chemical and biochemical processing industries are facing extensive challenges imposed by the rapidly changing market situation and the changes in the world 10 economy, increasing social pressure and tightening legislation on protection of our ecosphere and the huge pressure from shareholders on capital productivity of money invested in this industry.
The market situation in Europe and in North-America in particular is very though for the processing industries due to high costs (feedstock, energy, labour) and due to worldwide 15 installed capacities exceeding market demand. A specific additional problem for the European processing industries in this respect is that the European plants on the average already are relatively old and small scale in comparison to newly started plants and plants under construction in the Middle-East and Far-East. This makes the current competitive position of the European plants relatively weak. To a lesser extend this also applies for the North-20 American plants. The current situation for Europe and North-America may be expected to also extend to developing areas within the next decade.
Global competition has turned the market into a fully customer driven market the past decade. This implies that suppliers to this market are facing fierce competition where only those will survive that meet the following conditions: 25 - Deliver at low(est) cost - Deliver products that meet the requested specifications at a high quality level meeting imposed quality standards (Cpk-values, 6-Sigma, ...) - Deliver the requested volume(s) of products at the requested time - Cover a product portfolio that aligns with the fluctuations and changes in market 30 demand Market price of delivered products and services is a key decisive factor today for most customers. If a customer can choose from two or more vendors that deliver about the same quality and that can deliver the requested product volume at the requested time, he will select the supplier that reliably delivers at minimum cost. To be competitive in this market the 2 price of products and services is a key success factor. Too high a price directly implies that the orders will go to competition. Quality is an equally important key success factor. A supplier that delivers products that don’t meet requested specifications would not be selected. Most customers don’t want to build up stocks. Pressure on capital productivity at customer 5 side makes that suppliers are forced to deliver at demand of the customer. As a consequence suppliers have to be flexible in delivering varying product mixes and product volumes at relatively short notice. To meet this requirement a supplier has the possibility to build up large stock themselves, which of course is a very expensive way of working, or to move towards producing at demand thus minimizing internal stocks and consequently minimizing the capital 10 invested in materials and (semi-)manufactured products.
Market demand is very volatile today. Worldwide competition and the availability of a large production capacity worldwide make that customers can do their shopping globally in many cases. The available means of communication make that information is globally available without severe restrictions. Enabling very short product development cycles 15 strengthens market position of manufacturers. The short product development cycles create the opportunity for a manufacturer to discriminate from competition and to create competitive advantage. Very short product development cycles, so strong innovativeness, help manufacturers to follow volatility of the market. Like the current situation in semiconductors, consumer electronics, automotive and telecommunications also the process industries will be 20 facing the pressure from shortening product life cycles and the increasing sensitivity for time-to-market of new products. The manufacturers that have control over their full product development cycles and over their time-to-market will have a very significant competitive advantage. A break-through technology that enables very tightly controlled and fully predictable operation of processes and that furthermore enables instantaneous manipulation of 25 processes at demand will change the competitive game completely.
Today’s flexibility in the operation of processes in petrochemical, chemical and biochemical processing industries is limited by the lack of effective control handles for the processes. Current control of the processes in the petrochemical, chemical and biochemical processing industries is done by manipulation of one or more of the four main process 30 conditions that determine the ongoing processing in reactors and bio organisms: - Concentration of relevant reactants or nutrients - Pressure - Temperature 3 - Residence time
Manipulation of any of these conditions requires direct manipulation of a major mass or energy flow. These manipulations can only be realized with severe resolution, rate- and amplitude limitations. As a consequence, control of the processes can only be done within a 5 very restricted bandwidth, which does not or only hardly exceeds the natural bandwidth of the process (i.e. relatively long response times instead of instantaneous response) and within a very restricted dynamic range (i.e. range between largest possible response and minimum observable response is relatively small: <100).
10 Summary of the invention
These restrictions (as indicated above) in process operation severely limit both flexibility and achievable quality in the operation of processes. The resulting relatively long process start-up, shutdown and transition times make that processes have to be operated at relatively large volumes per batch of a product type to keep total costs per batch of good 15 product acceptably low. It hampers responsiveness of the industry to fluctuations in demand both with respect to volume as well as with respect to product types/ product specifications. The process industries require technology that preferably enables a direct response in manufacturing to specific demand coming from the market. Technology is needed that supports production transitions and recovery from process upsets in very short time intervals. 20 The technology needed is similar to the technology applied today in electronics, mechatronics, automotive and aerospace applications. The control techniques applied in these environments enable operation over very large dynamic ranges (e.g. audio and video equipment operating at signal to noise ratios up to 140 dB, which is equivalent to a ratio between largest possible response and minimum observable response of 10.000.000), very 25 large frequency ranges (e.g. servomechanisms having a bandwidth of up to 1000 times the natural bandwidth, electronic circuits having bandwidths of up to 100.000 times the natural bandwidth of the applied components) and at accuracy levels, which are extremely high compared to the basic specifications of the underlying process design (e.g. DVD players use weak, very light mechanical constructions that nevertheless are operated at positioning 30 accuracies of <500nm with very fast response times.
The main basic component that enabled the above mentioned high performance applications in electronics, mechatronics, automotive and aerospace is the transistor. The main characteristic of this transistor is that it can precisely manipulate a primary energy flow 4 (electrical current) almost instantaneously with a very low energy demanding manipulation (basis current or gate voltage manipulation) and with a very high resolution. This easy, accurate and very fast to realize manipulation enables the design of systems that can be virtually operated towards extreme conditions where the system would normally be damaged 5 completely, if such condition would be realized and persist even only a very short time. The very fast, easy to realize and robust manipulability of the system makes that the system can nevertheless be operated at conditions that intend to move the system very rapidly towards these extreme conditions, but where the movement is stopped or even reversed long before safety limits are exceeded. This today allows the design of e.g. cars where control systems 10 completely determine the dynamic behaviour, ease of driving, comfort and robustness at one hand and at the same time the use of remaining freedom in engine operation to minimize emissions and fuel consumption. This same technology allows the design of airplanes (fighters) that can make turns invoking accelerations that reach or easily can exceed the maximum g-forces a human pilot can handle without losing conscience.
15 The same technology also enabled the design of consumer electronics products like CD
players, DVD players, very fast access, high density hard disks, camera’s, video systems etc. that at one hand achieve incredible performance in terms of accuracy, response dynamics, reproducibility and reliability and at the same time almost everybody can afford to buy today due to the low prices. The possibility to manipulate systems very fast and to virtually drive to 20 steady state conditions that largely exceed the operating limits of the system make that the response characteristics of the system can be changed completely to make the system settle at desired operating conditions within a fraction of the natural response time of the system.
This possibility of very fast manipulation of the system also allows very accurate operation of the system and severe reduction of disturbances thus increasing the available 25 dynamic range within which the system can be operated.
The component that has had a major impact on our society the past 50 years, the electronic transistor, today does not have an equivalent in the chemical processing industry. It is possible however to create an equivalent component. The basis for this component is to be found in catalysts and enzymes. Catalysts and enzymes both influence the status and progress 30 of reactions in petrochemical, chemical and bio-chemical environments. Bottom line these components reduce the energy needed to make a reaction start or enable reactions to proceed at higher speed.
5
The basic effect of these components on the progress of a chemical reaction is similar to the basic effect of a transistor on an electrical current, when it is operating at a given operating condition. Affecting the activity of the catalyst or the enzyme has a same impact on initiation or progress of a reaction as manipulation of the basis current or gate voltage has on 5 the amount of current passing through the electronic transistor. Realizing manipulability of the catalyst or enzyme activity creates the “chemical transistor”.
The “chemical transistor” device paves the way towards extremely responsive, very high performance operation of processes in the processing industries. It will enable operation of processes at demand in an extremely flexible and highly automated way. As an example 10 the impact of the “chemical transistor” on a slurry loop polymerization process can be taken.
Today’s operation of this reactor is limited to the natural response dynamics of the process to realize process transitions between process grades. The resulting typical average transition time is approximately 4 hours for state-of-the-art industrial reactors. The “chemical transistor” applied in this process will enable a grade transition in seconds instead as a result of the 15 potential to initiate a direct controlled swing to the operating conditions required for the new grade. As another example the conversion in a chemical reactor can be taken (e.g. NH3 synthesis, catalytic Cracking, Styrene production, ...). Current reactor operation and today’s applied use of catalysts often limits conversions to a fraction only of full conversion. Techniques like trickle bed operation already allow a significant increase of conversion per 20 pass. Application of the “chemical transistor” will enable much larger conversions, depending upon the process, even up to 100% conversion in a single pass. The use of manipulable catalyst activity in a control loop enables operation of reactions at very tight specifications regarding conversions, heat production etc. Ultimately the application of the “chemical transistor” will take away the market restrictions felt in the European and North-American 25 process plants today. It will enable operation of processes at productivity conditions that are multiples of today’s. The impact on the market will be extreme as soon as the technology gets accepted and applied. The technology will enable development of completely new processes and process designs that can be operated at a fraction of the costs of today’s processes.
The thrust of the present proposal is to transfer the concept of the transistor to the field 30 of chemistry and improve the available bandwidth and control in small size chemical reactors. Doing so would open the perspective of unparalleled flexibility in operation as well as greater control over the fundamental processes at the heart of chemical processes, i.e. the catalytic surface.
6
An important ingredient in this philosophy is the replacement of the usual thermal activation of chemical processes by smarter, dynamical activation methods.
Traditionally, there are four variables used to control chemical processes: temperature, pressure, concentration and residence time (see also above). In this application we aim to add 5 a fifth degree of freedom: controlling the catalytic surface condition by smart activation. The direct local and dynamic influencing of the conditions at the catalytic sites, introduces a new and precise way of controlling reaction paths and their rates. This opens reaction pathways with involvement of reactive species in concentrations and configurations different than in the conventional steady-state approach of catalytic processes. Conventional reaction complexes 10 that need or create excess heat in order to run can be replaced by alternatives that operate highly energy efficient by precise activation of molecular states. Two of the considered smart activation approaches are non-thermal activation (NTA) and microsecond temperature pulsing. Fast electrical current pulsing (< 10'5s) may temporarily create a very local temperature spike at reactive sites, which influences the reaction paths. With NTA accelerated 15 electrons from field emission or surface plasma excite species locally and precisely and enable adsorption/reactions to take place on the catalyst. A closely related method that we propose is E-field pulsing to activate the catalytic surface in a way that is somewhat similar as in photo-catalysis.
For the actual methods to realize smart activation a variety of concepts is conceived. 20 The central theme is to actively steer the energy levels at the catalyst surface. Three methods in particular are proposed: smart activation by temperature spikes, by surface plasma and by E-field pulses.
Temperature spikes are created by a pulsed current through a layer of catalyst. By precise dimensioning of the heat flows in the system, pulses of for example 1000 K in 10'5 s 25 are created. The precise values required depend on the specific catalytic reaction. This form of actuation is based on well-known electrical engineering techniques and can be realized quickly. An initial setup will be created to demonstrate the effects of quickly and locally applying energy in chemical reactors. Examples of non-thermal activation (NTA) are discussed below.
30 Pre-defined electron energies are created by dedicated pulsed non-thermal plasma at ambient pressure at the surface of the catalyst (surface discharge or field emission). The challenge is to accelerate electrons to the optimum energy level for the activation of excited states. The energy of these states has to be in the range of the energy required to overcome the 7 barriers for chemisorption when the excited molecules strike the catalyst. Since the lifetime of many excited states of interest is short, the activation should occur at or near the surface of the catalyst.
Thirdly, E-field excitation is proposed, for the gas phase as well as for the solid-state 5 catalyst. It is suggested that similar to the mechanism that occurs with photo catalysis by the transfer of photon energy, an E-field pulse can deliver the energy to bring an electron across the band gap leaving a hole in the valence band. Local E-field strength and mobility of the electrons may determine the energy transferred to the free electrons created. The activation mechanism of reactants may subsequently depend on the efficient energy transfer by virtue of 10 electron-to-electron impulse transfer. Catalytic materials containing P-type, N-type or PN junctions can be investigated for their effectiveness in creating electron-hole pairs that serve to initiate the reactions on the cat surface. Alternatively, an E-field pulse acting on the gas phase can shift the energy levels of the valence electrons of the gas molecules to enhance “dissociative bonding” between surface molecules and gas molecules. In comparison with the 15 surface plasma, this third concept does not need ionization. This saves energy compared to the plasma activation technique, (note however that with the plasma-activation technique, the electron, once created, can be used many times).
Since the new activation technique has the potential to greatly enhance chemisorption, the range of catalyst materials does not have to be restricted anymore to the traditional well 20 adsorbing metals. Instead, the choice of catalytic material can be much widened and focused on e.g. optimum reaction and desorption properties.
Earlier work on plasma-assisted catalysis encountered a few major difficulties: • Absence of precisely tuned activation • Ineffective creation of radicals 25 • Weak contact between most of the plasma and the catalytic surface.
The present approach entirely circumvents these problems and is therefore incomparable with this older work. The invention is also distinct from so-called non-thermal plasma chemistry because it acts exclusively at the catalyst surface and it uses pre-defined energy and E-field. It is also far from microwave chemistry which is steady state and only 30 proven to add heat.
The chemical transistor concept aims to precisely activate specific reactions in a reaction complex. The following reaction complexes have the main focus during the start of this invention.
8 • Non-oxidative methane coupling: Methane activation requires high temperatures, while the hydrogenation runs better at low temperatures. The principle idea here is to stimulate methane adsorption by tuned energy pulses while allowing hydrogenation to take place in between the pulses.
5 • Fischer-Tropsch synthesis: Using syngas instead of methane makes it easier to create higher hydrocarbons, but still has great selectivity issues. By having a low base temperature, precise activation can allow us to influence the product distribution.
• Polymerization: Here we have three reaction types, initiation, propagation and termination. Experiments have indicated that the chemical transistor pulsing concept allows to 10 trigger initiation reactions, after which propagation can easily take place at low temperatures and low chance of termination.
Control over the molecular weight distribution is what is aimed for in this reaction scheme.
Hence, in a first aspect, the invention involves a process for the production of a 15 compound comprising: a. providing a reactor with a reactor volume containing a catalyst on a support; b. providing one or more starting products in the reactor volume while maintaining the reactor volume under non-reactive conditions for the one or more starting products; c. subsequently providing an energy pulse to the reactor volume, wherein the pulse 20 contains sufficient energy to start a catalytic reaction of the one or more starting products to provide a reaction product comprising the compound; and d. subsequently removing the reaction product from the reactor volume.
Hence, with a relatively short (single) pulse, designed to let the starting products react to the desired end product in the presence of the catalyst, the desired end product may be 25 obtained. After the pulse, the reaction product is removed, and new starting product may be introduced in the reactor volume.
The conditions within the reactor volume are generally chosen that under nominal conditions, the desired reaction does not or does hardly occur. Further, the catalyst, such as a metal, a metal oxide, or an enzyme, is arranged at well defined positions within the reactor 30 volume. A major difference with “process intensification” is that the energy used to bring valence electrons of the catalyst in the excited state, and thereby activation of the reactants to react, is done by well defined energy input to the catalyst or reactants. The energy within the pulse is well defined and is adjusted to the energy needed to activate the starting products.
9
The activated starting products react then to the desired end products. The energy provided to the active part of the reactor volume does thus directly lead to the reaction, which leads to a high efficiency. A good transport of the starting products and reaction product may therefore be of importance, because the reactions may, dependent upon the frequency of the energy 5 pulses, proceed fast. Material transport is therefore adjusted to the reaction.
Now, it appears there is a fifth degree of freedom: the frequency and energy content of the pulses.
This degree of freedom may be of importance to provide well controllable and predictable processes. Due to the nominal non-reactive conditions, the reactions may be 10 relatively safe. The reaction may not further be determined by the statistics of the velocity distribution of the molecules, but by well defined and targeted energy input at the catalyst.
Hence, the catalyst is activated by the energy, and the reaction may take place since the catalyst, due to the energy pulse, activates the starting products to react.
The starting products may be chosen from the group consisting of gas and liquid. At the 15 nominal conditions, one or more starting products may be introduced in the reactor volume. These one or more starting products may be gaseous at nominal conditions, may be liquid at nominal conditions or one or more may be gaseous and one or more may be liquid at nominal conditions. The term “nominal conditions” herein refers to the state wherein the reactor volume is between the energy pulses, i.e. in substantially non-reactive conditions for the 20 starting product(s).
In a specific embodiment, the energy pulse has a pulse width in the range of 10 ps or less, such as 5 ps or less, like 1 ps or less. The energy pulse may also be a composed pulse, i.e. a pulse that has a pulse width wherein different energy amounts may be provided during subset times of the pulse width. For instance, a pulse of 1 ps might consist of a pulse having 25 width of 500 ns, having a specific energy, followed by a pulse having also a width of 500 ns, having another specific energy.
The (sub) pulse width may also be smaller, such as in the range of about 5-500 ns. By choosing the pulse energy, specific pulse width and optional pulse composition, the desired product may be obtained, or may even be created step by step (composed pulse). In general, 30 the (sub) pulse width may be larger than about 0.1 ns, such as equal to or larger than 1 ns.
In a further embodiment, the process further involves repeating one or more times procedures b-d. This will generally be the case. The frequency of the pulses may for instance be in the order of 0.01-50000 Hz, such as in the range of 0.1-5000 Hz, which may be “short” 10 enough to relax to the nominal state, remove the reaction product and introduce new starting product(s).
Exemplary, the energy pulse has a pulse energy in the range of 0.01 - 500 mJ, like for instance 0.1-100 mJ. For instance, 0.01-500 mJ/cm2 catalyst surface may be provided per 5 energy pulse.
In a first embodiment, the process involves providing heat pulses, respectively, as energy pulses. The catalyst (surface) is temporarily heated to provide the desired energy within the pulse width. In this way, the reaction products react to the desired intermediate or end product (effluent) (indicated as “reaction product”). The reaction product comprises the 10 (target) compound, but may in addition also comprise other (undesired) compounds. Hence, the term “reaction product” may also refer to reaction product mixture”.
In another embodiment, the process includes providing a surface plasma (pulse) to provide the energy pulse. In yet another embodiment, the process involves providing a temporary electrical field (pulse) to provide the energy pulse.
15 Preferably, the active reactor volume is in the range of 1 pi.- 1 1.
In a specific embodiment, the reactor is a monolithic reactor comprising reaction volumes of 1 pi- 1 ml.
The catalyst may for instance be a metal surface, it may also be a metal oxide (surface), or a surface of a support with metal(oxide) sites on the surface. Alternatively, or additionally, 20 the catalyst may also be an enzyme.
In a further aspect, the invention provides a micro reactor for performing a process (such as described above) for the production of a compound comprising: a. a micro reactor volume comprising a catalyst on a support; b. one or more controllable ports to the reactor volume, arranged to allow one or 25 more starting products for the production of the compound enter the reactor volume and arranged to remove a reaction product comprising the compound; and c. one or more energy pulses generator(s), arranged to provide one or more energy pulses having a pulse width in the range of 10 ps or less, such as 1 ps or less and having an energy in the range of 0.01-500 mJ per pulse to the reactor volume.
30 Especially, the micro reactor may further comprise a controller arranged to control the one or more controllable ports and the energy pulse generator.
11
Brief description of the drawings
Embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts, and in which: 5 Figure la schematically depicts the general layout of the invention.
Figure lb further gives an embodiment in which the catalyst reaction is controlled by pulsed-wise temperature control at the catalyst surface.
A general description of a second embodiment is shown in figure lc, where the reaction is controlled by a electromagnetic field pulses across the catalyst surface and the reaction 10 volume. The third example reaction control mechanism given here is the plasma-controlled principle, outlined in figure Id.
Figure le gives an impression of the time scales involved in the catalytic reaction process.
15 Detailed description
Figure la schematically depicts the general layout of the invention. The reactor 1 comprises a reactor envelope 2, with, for example, a first feed channel 3 for supply of reaction component 4 and optionally a second feed channel 5 for supply of reaction component 6. In addition the reactor is provided with a discharge channel 7 for discharge of reaction products 20 8. The feed and discharge channels may be provided with gates/valves for controlled supply and discharge of components and products. The reactor has a reactor volume 20. Inside the reactor volume 20 a catalyst carrier material 9 (herein also indicated as support) with catalyst layer 10 are mounted, adjacent to the reaction zone 11. The catalyst layer 10 can be energised by various means, for example by a dissipative electrical heating, electromagnetic wave 25 energy, microwave, plasma, acoustic and thermo-acoustic and other radiation means (light, nuclear).
Operation of the chemical transistor will now be elaborated, by using a thermal activation principle, outlined in figure lb for the oxidation of CO to CO2, in an atmosphere of Carbon monoxide (CO), Nitrogen (N2), Hydrogen (H2) and Oxygen (02). It is known that 30 the objective reaction (O2 + 2CO —► 2CO2) is hard to accomplish, without the undesired side reaction (C0+H20<->H2+C02; 2H2 + O2 —* 2H2O) to occur.
In this embodiment, the reactor volume 20 further comprises an activation layer 12, comprising a thin electrical heating element. In this schematically depicted embodiment, the 12 activation layer 12 is placed between the catalyst carrier 9 and catalyst 10. Further, the activation layer 12 is connected through a power line 13 to a pulse generator 14.
Prior to pulse-wise operation, the reactor 1 is brought into sub-critical conditions regarding pressure and temperature for the objective reaction (O2 + 2CO —> 2CO2) to take 5 place. During operation, prior to each pulse, reactor feed CO, N2, O2 and H2 are transported into the reactor volume 20 and positioned adjacent to the catalyst surface. This process step may for instance take 10-1000 ms. In the next process step, the activation layer 12 is pulse-wise energised, thereby bringing the catalyst layer 10 and adjacent reaction zone 11 at the desired temperature conditions for the catalytic reaction to initiate and take place. This 10 activation process step is kept very short (order of magnitude of for instance 1 ps or less); sufficiently long for the chemical reaction to take place and yet short enough to suppress undesired side reactions (e.g. 2¾ + O2 —> 2H2O; C0+H20<->H2+CC>2). The energy required in this case typically is in the range of 0.1-5 mJ/cm2. After the chemical reaction process step, reaction products and other gases are discharged from the reactor and simultaneously a fresh 15 load of components are fed into the reactor.
Another example, using electromagnetic field activation is described in a more general sense (without a specific objective reaction scheme) in figure lc. In this embodiment the reaction zone 11 adjacent to the catalyst is located between a first electrode 16 (for instance positioned between the catalyst carrier 9 and the catalyst 10), and a second electrode 17. The 20 electrodes are connected to an electrical pulse generator 14 by means of connectors 13 and 18. In this example the electrical field (for instance up to 10 kV/mm) activates the catalyst reaction by directly exiting the valence electrons to a higher energy state (typically 0.5-10 eV), necessary for the reaction to take place. As in the previous example the pulse-wise excitation and chemical reaction takes place in a much shorter time span (< 10 ps) than 25 the physical time scale necessary to transport and position the reaction components and reaction products.
Figure Id outlines a third activation principle, based on plasma generation at the catalyst surface. A low temperature plasma is generated at the surface of the catalyst 10, in the reaction zone 11, by means of an electrode-grid 19, for instance arranged between the catalyst 30 10 and catalyst carrier 9. The electrode 19 is connected to a pulse generator 14 by means of connection 13. By energising the electrode by short pulses (such as in the order 1-10 ps), free electrons are generated at the catalyst surface, inside the reaction zone 11. These free electrons with energies typically in the range of 0.5 eV up to 10 eV, provide the activation 13 energy for the molecules to react and result in the objective reaction. As explained above, energy may be transferred by efficient (free) electron-to-electron impulse transfer.
The aspect of timescale separation between chemical activation (reaction) process and physical transport process is further explained in figure le. In this time-intensity graph the 5 process activation pulses are displayed in time (horizontal axis) and intensity (vertical axis). Pulses are generated at time interval 31 (=l/process-frequency), at duration 30 and at intensity 32. This figure illustrates the difference in activation -chemical- time scale (30) and physical time scale (31), a difference of at least one order of magnitude (factor 10) to several orders of magnitude will be applied. The difference is dominated by the -relatively short-10 time needed for a chemical reaction complex to complete (Pulse-width) versus the time needed for physical transport of mass and heat.
In all examples given, activation of the objective reaction takes place in a (chemical) time scale much shorter than the physical time scale associated with the transport and positioning of the reaction components and products. Furthermore, the activation energy is 15 relatively small, compared to the total energy involved. These features constitute the main characteristics of the invention, having the objective to provide a catalyst chemical reactor that is energy efficient, compact and high yield.
Specific embodiments, are described below (and numbered for the sake of clarity): 1. A process for the production of a compound comprising: 20 a. providing a reactor with a reactor volume containing a catalyst on a support; b. providing one or more starting products in the reactor volume while maintaining the reactor volume under non-reactive conditions for the one or more starting products; c. subsequently providing an energy pulse to the reactor volume, wherein the 25 energy pulse contains an energy sufficient to start a catalytic reaction of the one or more starting products to provide a reaction product comprising the compound, wherein the energy pulse has a pulse width in the range of 10 ps or less; and d. subsequently removing the reaction product from the reactor volume.
30 2. The process according to process embodiment 1, wherein the energy pulse has a pulse energy in the range of 0.01-500 mJ.
3. The process according to any one of the preceding process embodiments, comprising providing a repetitive heat pulse as energy pulse.
14 4. The process according to any one of the preceding process embodiments, comprising providing a surface plasma to provide the energy pulse.
5. The process according to any one of the preceding process embodiments, comprising providing a temporary electrical field to provide the energy pulse.
5 6. The process according to any one of the preceding process embodiments, wherein the reactor volume is in the range of 1 pi - 1 1.
7. The process according to any one of the preceding process embodiments, wherein the reactor is a monolithic reactor comprising reaction volumes of 1 pi - 1 ml.
8. The process according to any one of the preceding process embodiments, wherein the 10 catalyst is an enzyme.
9. The process according to any one of the preceding process embodiments, comprising repeating one or more times procedures b-d.
10. A micro reactor for performing a process for the production of a compound comprising: 15 a. a micro reactor volume comprising a catalyst on a support; b. one or more controllable ports to the reactor volume, arranged to allow one or more starting products for the production of the compound enter the reactor volume and arranged to remove a reaction product comprising the compound; and 20 c. one or more energy pulses generator, arranged to provide one or more energy pulses having a pulse width in the range of 10 ps or less and having an energy in the range of 0.01-500 mJ/cm2 catalyst surface to the reactor volume.
11. The micro reactor according to reactor embodiment 10, further comprising a controller arranged to control the one or more controllable ports and the energy pulse generator.
25 The term “substantially” herein, such as in “substantially flat” or in “substantially consists”, etc., will be understood by the person skilled in the art. In embodiments the adjective substantially may be removed. Where applicable, the term “substantially” may also include embodiments with “entirely”, “completely”, “all”, etc. Where applicable, the term “substantially” may also relate to 90% or higher, such as 95% or higher, especially 99% or 30 higher, including 100%. The term “comprise” includes also embodiments wherein the term “comprises” means “consists of’.
Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for 15 describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
5 The devices herein are amongst others described during operation. As will be clear to the person skilled in the art, the invention is not limited to methods of operation or devices in operation.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative 10 embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. Use of the verb "to comprise" and its conjugations does not exclude the presence of elements or steps other than those stated in a claim. The term “and/or” includes any and all combinations of one or more of the associated listed items. The article "a" or "an" preceding an element 15 does not exclude the presence of a plurality of such elements. The article "the" preceding an element does not exclude the presence of a plurality of such elements. The invention may be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer. In the device claim enumerating several means, several of these means may be embodied by one and the same item of hardware. The mere fact that 20 certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.

Claims (11)

1. Een proces voor de productie van een stof, omvattende: a. het verschaffen van een reactor met een reactorvolume omvattende een 5 katalysator op een drager; b. het toevoeren van een of meer componenten in het reactorvolume, gehouden onder niet-reactieve condities voor de een of meerdere componenten; c. het vervolgens toedienen van een energiepuls aan het reactorvolume, waarbij de energiepuls voldoende energie bevat om de katalytische reactie tussen de de 10 een of meerdere componenten te doen starten, met als resultaat een reactieproduct omvattende de stof, waarbij de pulsbreedte kleiner of gelijk is aan 10 ps; en d. het vervolgens het verwijderen van het reactieproduct uit het reactorvolume.A process for the production of a substance, comprising: a. Providing a reactor with a reactor volume comprising a supported catalyst; b. feeding one or more components into the reactor volume held under non-reactive conditions for the one or more components; c. subsequently applying an energy pulse to the reactor volume, wherein the energy pulse contains sufficient energy to start the catalytic reaction between the one or more components, resulting in a reaction product comprising the substance, the pulse width being less than or equal to 10 ps; and d. then removing the reaction product from the reactor volume. 2. Proces volgens conclusies 1, waarbij de energiepuls een energie-inhoud heeft in de 15 range van 0.01-500 mJ.2. Process according to claim 1, wherein the energy pulse has an energy content in the range of 0.01-500 mJ. 3. Proces volgens een van voorafgaande conclusies, omvattende het toedienen van een warmtepuls als energiepuls.Process according to any of the preceding claims, comprising applying a heat pulse as an energy pulse. 4. Proces volgens een van voorafgaande conclusies, omvattende het verschaffen van een oppervlakteplasma voor het toedienen van de energiepuls.The process of any preceding claim, comprising providing a surface plasma for applying the energy pulse. 5. Proces volgens een van voorafgaande conclusies, omvattende het verschaffen van een transient electrisch veld voor het toedienen van de energiepuls.The process according to any of the preceding claims, comprising providing a transient electric field for applying the energy pulse. 6. Proces volgens een van voorafgaande conclusies, waarbij het reactorvolume een grootte heeft van 1 jllI — 1 1.Process according to any of the preceding claims, wherein the reactor volume has a size of 1 µl - 1 l. 7. Proces volgens een van voorafgaande conclusies, waarbij de reactor monolithisch is 25 met een reactorvolume van 1 jul — 1 ml.7. Process according to any of the preceding claims, wherein the reactor is monolithic with a reactor volume of 1 Jul - 1 ml. 8. Proces volgens een van voorafgaande conclusies, waarbij de katalysator een enzym is.The process according to any of the preceding claims, wherein the catalyst is an enzyme. 9. Proces volgens een van voorafgaande conclusies, die een herhaling van de procedures b-d omvat.The process according to any of the preceding claims, comprising a repeat of the procedures b-d. 10. Een micro-reactor voor het doen tot stand komen van een proces voor de productie 30 van een stof, omvattende: a. een microreactor omvattende een katalysator op een drager; b. een of meer bestuurbare poorten naar het reactorvolume, geplaatst voor toevoer van componenten ten behoeve van de productie van een reactieproduct omvattende de stof, en geplaatst voor afvoer van het reactie-product; en c. een energiepulsgenerator, voor toedienen aan het reactorvolume van een of 5 meer energiepulsen met tijdsduur in de orde van ten hoogste 10 ps met een energie-inhoud in de orde van 0.01-500 mJ/cm2 katalysatoroppervlak.10. A micro-reactor for effecting a process for the production of a substance, comprising: a. A micro-reactor comprising a supported catalyst; b. one or more controllable ports to the reactor volume, placed for supply of components for the production of a reaction product comprising the substance, and placed for discharge of the reaction product; and c. an energy pulse generator, for administering to the reactor volume one or more energy pulses with a duration on the order of at most 10 ps with an energy content on the order of 0.01-500 mJ / cm 2 of catalyst surface. 11. Microreactor volgens conclusie 10, bovendien omvattende een regelaar voor aansturing van de regelbare poorten en energiepulsgenerator.A microreactor according to claim 10, further comprising a controller for controlling the controllable ports and energy pulse generator.
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