Millisecond reactor

Scale-up of structured reactors is usually easier than for packed-bed reactors. The major point is that the hydrodynamics are independent of the scale of the reactor (assuming a good inlet device). When the radial temperature profile is also independent of the scale, scale-up is straightforward. This is the case for millisecond reactors. In these reactors, rates are very high as a consequence, in exothermic reactions they operate adiabatically. So they scale easily. 

In spite of the commercial successes of these two millisecond reactors, few processes other than NH3 oxidation (a superoxidation) and HCN synthesis (oxidative dehydrogenation or ammoxidation) have been carried out on a large scale. In the automotive catalytic converter, contact times over noble metals on wash coated extended ceramics are used with contact times of -0.1 sec with temperatures of 400°C. 

Oxidative dehydrogenation is kinetically fast and may relieve this limitation [6]. Previous research has shown that substantial amounts of olefins are formed by catalytic oxidative dehydrogenation in a high temperature (1000°C), short contact time (1-10 milliseconds) reactor for small alkanes [7, 8]. 

Schmidt L.D., Klein E.J., O Connor R.P., and Tummala S. (2001) Production of hydrogen in millisecond reactors combination of partial oxidation and water-gas shift . Abstracts of Papers of the American Chemical Society, 222 (FUEL Part 1) 111. 

Schmidt LD. Modeling millisecond reactors. In Iglesia E, Fleish TH, editors. Proceedings of the 6th natural gas conversion symposium. Girdwood, Alaska, 2001. Studies in surface science and catalysis. Natural gas conversion VI, vol. 136. Amsterdam-London-New York-Oxford-Paris-Shannon-Tokyo Elsevier Science B.V 2001. 

Hydrocarbon, typically natural gas, is fed into the reactor to intersect with an electric arc stmck between a graphite cathode and a metal (copper) anode. The arc temperatures are in the vicinity of 20,000 K inducing a net reaction temperature of about 1500°C. Residence time is a few milliseconds before the reaction temperature is drastically reduced by quenching with water. Just under 11 kWh of energy is required per kg of acetylene produced. Low reactor pressure favors acetylene yield and the geometry of the anode tube affects the stabiUty of the arc. The maximum theoretical concentration of acetylene in the cracked gas is 25% (75% hydrogen). The optimum obtained under laboratory conditions was 18.5 vol % with an energy expenditure of 13.5 kWh/kg (4). 

A conventional FCC unit can be an olefin machine with proper operating conditions and hardware. Catalysts with a low unit cell size and a high silica/alumina ratio favor olefins. Additionally, the addition of ZSM-5, with its lower acid site density and very high framework silica-alumina ratio, converts gasoline into olefins. A high reactor temperature and elimination of the post-riser residence time will also produce more olefins. Mechanical modification of the FCC riser for millisecond cracking has shown potential for maximizing olefin yield. 

Almost all flows in chemical reactors are turbulent and traditionally turbulence is seen as random fluctuations in velocity. A better view is to recognize the structure of turbulence. The large turbulent eddies are about the size of the width of the impeller blades in a stirred tank reactor and about 1/10 of the pipe diameter in pipe flows. These large turbulent eddies have a lifetime of some tens of milliseconds. Use of averaged turbulent properties is only valid for linear processes while all nonlinear phenomena are sensitive to the details in the process. Mixing coupled with fast chemical reactions, coalescence and breakup of bubbles and drops, and nucleation in crystallization is a phenomenon that is affected by the turbulent structure. Either a resolution of the turbulent fluctuations or some measure of the distribution of the turbulent properties is required in order to obtain accurate predictions. 

Dream reactions can be performed using chemical micro process engineering, e.g., via direct routes from hazardous elements [18]. The direct fluorination starting from elemental fluorine was performed both on aromatics and aliphatics, avoiding the circuitous Anthraquinone process. While the direct fluorination needs hours in a laboratory bubble column, it is completed within seconds or even milliseconds when using a miniature bubble column. Conversions with the volatile and explosive diazomethane, commonly used for methylation, have been conducted safely as well with micro-reactors in a continuous mode. 

Micro reactors show, under certain conditions, low axial flow dispersion reactions with unstable intermediates can be carried out in a fast, stepwise manner on millisecond time-scales. Today s micro mixers mix on a millisecond scale and below [40]. Hence in micro reactors reactions can be carried out in the manner of a quench-flow analysis, used for determination of fast kinetics [93]. 

For gas phase heterogeneous catalytic reactions, the continuous-flow integral catalytic reactors with packed catalyst bed have been exclusively used [61-91]. Continuous or short pulsed-radiation (milliseconds) was applied in catalytic studies (see Sect. 10.3.2). To avoid the creation of temperature gradients in the catalyst bed, a single-mode radiation system can be recommended. A typical example of the most advanced laboratory-scale microwave, continuous single-mode catalytic reactor has been described by Roussy et al. [79] and is shown in Figs. 10.4 and... 

Unlike SRE, the POE reaction for H2 production has been reported so far only by a few research groups.101104-108 While Wang et al. os and Mattos et r//.104-106 have studied the partial oxidation of ethanol to H2 and C02 (eqn (18)) at lower temperatures, between 300 and 400 °C using an 02/EtOH molar ratio up to 2, Wanat et al.101 have focused on the production of syngas (eqn (19)) over Rh/Ce02-monolith catalyst in a catalytic wall reactor in millisecond contact time at 800 °C. Depending on the nature of metal catalyst used and the reaction operating conditions employed, undesirable byproducts such as CH4, acetaldehyde, acetic acid, etc. have been observed. References known for the partial oxidation of ethanol in the open literature are summarized in Table 6. 

ISOTOPES There are 49 isotopes of tin, 10 of which are stable and range from Sn-112 to Sn-124. Taken together, all 10 stable isotopes make up the natural abundance of tin found on Earth. The remaining 39 isotopes are radioactive and are produced artificially in nuclear reactors. Their half-lives range from 190 milliseconds to 1x10+ years. 

ISOTOPES There are a total of 64 isotopes of promethium with half-lives ranging from two milliseconds to over 17 years. There is no stable isotope, but Pm-147 with a half-life of 2.64 years is considered the most stable. No promethium is found naturally in the Earth s crust. All of it is produced artificially from the leftover residue in nuclear reactors. 

Figure 3-7 Plot of nominal space times (or reactor residence times) required for several important industrial reactors versus the nominal reactor temperatiwes. Times go from days (for fermentation) down to milliseconds (for ammonia oxidation to form nihic acid). The low-temperature, long-time processes involve liquids, while the high-temperature, short-time processes involve gases, usually at high pressures.

Temporal analysis of products (TAP) reactor systems enable fast transient experiments in the millisecond time regime and include mass spectrometer sampling ability. In a typical TAP experiment, sharp pulses shorter than 2 milliseconds, e.g. a Dirac Pulse, are used to study reactions of a catalyst in its working state and elucidate information on surface reactions. The TAP set-up uses quadrupole mass spectrometers without a separation capillary to provide fast quantitative analysis of the effluent. TAP experiments are considered the link between high vacuum molecular beam investigations and atmospheric pressure packed bed kinetic studies. The TAP reactor was developed by John T. Gleaves and co-workers at Monsanto in the mid 1980 s. The first version had the entire system under vacuum conditions and a schematic is shown in Fig. 3. The first review of TAP reactors systems was published in 1988. 

The high heat transfer rates achievable in micro heat exchangers and reactors avoid unfavorable reaction conditions resulting from hot spots or thermal runaway effects. An optimum temperature or temperature profile for the reaction can be chosen with respect to spatial distribution and time. Thus, a fast-flowing fluid element can be cooled down or heated up very rapidly, in fractions of a millisecond. Because of the small thermal mass of microdevices, a periodic change of temperature of the reactor can be realized, with a typical time constant of some seconds. All these examples offer possibilities to improve yield and selectivity. 

L. D. Schmidt, Millisecond Catalytic Wall Reactors Dehydrogenation... 

Acetylene may be produced from light hydrocarbons and naphthas by injecting inert combustion gases directly into the reacting stream in a flame reactor. Figure 19-13a and d shows two such devices Fig. 19-13 shows a temperature profile (with reaction times in milliseconds). 

Wire Gauzes Wire screens are used for very fast catalytic reactions or reactions that require a bulk noble metal surface for reaction and must be quenched rapidly. The nature and morphology of the gauze or the finely divided catalyst are important in reactor design. Reaction temperatures are typically high, and the residence times are on the order of milliseconds. 

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