Time, residence

Residence time is reduced by increasing the feed flowrate, but the flow conditions in the furnace tubes and soaking drum are also modified. 

In coil visbreaking, the residence time of the feed in the furnace is of 2-5 min. 

At the entrance, the gas phase consists mainly of steam. Due to cracking reactions and partial vaporization along the length, the fraction of gas phase increases. 

Providing adequate residence time is a primary consideration in arrangements that avoid vapor in liquid outlets. Such arrangements t )-ically include bottom sumps, chimney trays, external side-drawoff drums, or surge drums. Sufficient residence time must be provided in the liquid-drawoff sump for one or more reasons  

To disentrain vapor contained in the sump liquid. Entrained vapor bubbles may lead to downstream pump cavitation and to choking in downstream pipelines. 

To buffer downstream units from upstream and column upsets. This is most important when the sump is feeding sensitive units such as furnaces. 

To buffer the column from downstream upsets. This is most important if the liquid is feeding a downstream unit by direct pressure, and the pressure difference between the two is small. 

To give the operator sufficient time to take corrective action if common upsets occur (e.g., pump trips, level lost or gained too fast). 

The main limitation of HEX reactors is the short residence time, typically from a few seconds to a few minutes. Indeed, the apparatuses are smaller than the traditional ones and fast flow velocities are necessary in order to maintain good level of heat-transfer coefficients. However, as described in the previous paragraph, the highlighted transfer properties of HEX reactors allow us to operate in a few minutes, whereas it takes many hours in batch or semibatch mode. 

Batch reactor with outer heat exchanger 

The literature proposes a relatively large number of HEX reactors that have been designed and built of different materials such as glass, stainless steel, polyether ether ketone (PEEK), and silicon carbide (SiC). A presentation can be found in Amdoimaz et al. [13]. 

In the following part, four reactors that have been extensively studied in our lab are described the open plate reactor (OPR) - the Alfa-Laval reactor technology (ART ) plate reactor, the Shimtec reactor from Chart Industries, the Corning (glass reactor), and the DeanHex reactor which has been constructed with SiC and stainless steel. 

Due to the existence of a high thermal gradient along a pyrolysis fiimace tube, it is difficult to pinpoint the concept of residence time. A frequent solution is to define an 

Xf — molar conversion calculated from the molar flow rates of the reactant at the reactor inlet iVj and outlet JVi  

In the presence of a temperature gradient the rate constant varies between the inlet and outlet of the reactor according to Arrhenius law  

For an isothermal reactor operating at the fmai temperature 7 at the pyrolysis tube exit, the equivalent residence time which serves to achieve an identical conversion 

However in the 1980 s, the latest furnace designs offered times ranging from 0.2-0.08 s. Millisecond technology, developed by Kellogg Co and industrialized by Idemitsu Petrochemical Company at their Chiba factory in 1985 is operating at the lowest end of that range. 

The chemical changes that can occur during processing and effect product performances include (1) continued polymerization and cross-linking, which increases viscosity (2) depolymerization or damaging of molecules, which reduces viscosity and (3) 

Another exception to the known mechanisms of conventional chemistry may arise when dominance of surface reactions is achieved in micro reactors. This holds for all catalytic reactions on solid contacts. Beyond that, it was shown that some formerly homogeneous bulk reactions may become heterogeneous when carried out in a micro reactor owing to the very large surface-to-volume ratio [155,171,172], 

Experimental protocols are amenable to change by using micro-flow conditions. 

One commonly found feature is a reduction in process times, simply because flow conditions allow a faster sequence of all necessary processing steps such as mixing and completion of reaction and promote reaction by optimized transport properties. 

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In the second model (Fig. 2.16) the continuous well-stirred model, feed and product takeoff are continuous, and the reactor contents are assumed to he perfectly mixed. This leads to uniform composition and temperature throughout. Because of the perfect mixing, a fluid element can leave at the instant it enters the reactor or stay for an extended period. The residence time of individual fluid elements in the reactor varies. 

Increasing the pressure of irreversible vapor-phase reactions increases the rate of reaction and hence decreases reactor volume both by decreasing the residence time required for a given reactor conversion and increasing the vapor density. In general, pressure has little effect on the rate of liquid-phase reactions. 

Solution We wish to avoid as much as possible the production of di- and triethanolamine, which are formed by series reactions with respect to monoethanolamine. In a continuous well-mixed reactor, part of the monoethanolamine formed in the primary reaction could stay for extended periods, thus increasing its chances of being converted to di- and triethanolamine. The ideal batch or plug-flow arrangement is preferred, to carefully control the residence time in the reactor. 

However, the laboratory data seem to indicate that a constant concentration in the reactor to maintain 63 percent sulfuric acid would be beneficial. Careful temperature control is also important. These two factors would suggest that a continuous well-mixed reactor is appropriate. There is a conflict. How can a well-defined residence time be maintained and simultaneously a constant concentration of sulfuric acid be maintained ... 

By contrast with ideal models, practical reactors must consider many factors other than variations in temperature, concentration, and residence time. Practical reactors deviate from the three idealized models but can be classified into a number of common types. 

Because the characteristic of tubular reactors approximates plug-flow, they are used if careful control of residence time is important, as in the case where there are multiple reactions in series. High surface area to volume ratios are possible, which is an advantage if high rates of heat transfer are required. It is sometimes possible to approach isothermal conditions or a predetermined temperature profile by careful design of the heat transfer arrangements. 

Gas-liquid mixtures are sometimes reacted in packed beds. The gas and the liquid usually flow cocurrently. Such trickle-bed reactors have the advantage that residence times of the liquid are shorter than in countercurrent operation. This can be useful in avoiding unwanted side reactions. 

Fixed-bed reactors in the form of gas absorption equipment are used commonly for noncatalytic gas-liquid reactions. Here the packed bed serves only to give good contact between the gas and liquid. Both cocurrent and countercurrent operations are used. Countercurrent operation gives the highest reaction rates. Cocurrent operation is preferred if a short liquid residence time is required. 

Achieving complete conversion of FEED to PRODUCT in the reactor usually requires an extremely long residence time, which is normally uneconomic (at least in continuous processes). Thus, if there is no byproduct formation, the initial reactor conversion is set to be around 95 percent, as discussed in Chap. 2. The reactor effluent thus contains unreacted FEED and PRODUCT (Fig. 4.1a). 

In aerobic processes, the mean sludge residence time is typically 5 to 10 days. The hydraulic residence time is typically 0.2 to 0.3 days. Suspended growth aerobic processes are capable of removing up to 95 percent of BOD. 

Influence of operating conditions This concerns the temperature, the pressure and the residence time. The more severe the conditions are, the harder is the coke produced. 

The conversion takes place at high temperature (820-850°C) and very short residence time (hundredth of seconds) in the presence of steam. The by-products are hydrogen, methane and a highly aromatic residual fuel-oil. 

Catalytic cracking is a key refining process along with catalytic reforming and alkylation for the production of gasoline. Operating at low pressure and in the gas phase, it uses the catalyst as a solid heat transfer medium. The reaction temperature is 500-540°C and residence time is on the order of one second. 

As well as preventing liquid carry over in the gas phase, gas carry undef must also be prevented in the liquid phase. Gas bubbles entrained in the liquid phase must be given the opportunity (or residence time) to escape to the gas phase under buoyancy forces. 

The ease with which small gas bubbles can escape from the liquid phase is determined by the liquid viscosity higher viscosities imply longer residence times. Typical residence times vary from, some 3 minutes for a light crude to up to 20 minutes for very heavy crudes. 

Studies of inelastic scattering are of considerable interest in heterogeneous catalysis. The degree to which molecules are scattered specularly gives information about their residence time on the surface. Often new chemical species appear, whose trajectory from the surface correlates to some degree with that of the incident beam of molecules. The study of such reactive scattering gives mechanistic information about surface reactions. 

Ref. 205). The two mechanisms may sometimes be distinguished on the basis of the expected rate law (see Section XVni-8) one or the other may be ruled out if unreasonable adsorption entropies are implied (see Ref. 206). Molecular beam studies, which can determine the residence time of an adsorbed species, have permitted an experimental decision as to which type of mechanism applies (Langmuir-Hinshelwood in the case of CO + O2 on Pt(lll)—note Problem XVIII-26) [207,208]. 

Figure A3.14.3. Example bifurcation diagrams, showing dependence of steady-state concentration in an open system on some experimental parameter such as residence time (inverse flow rate) (a) monotonic dependence (b) bistability (c) tristability (d) isola and (e) musliroom.

Many optical studies have employed a quasi-static cell, through which the photolytic precursor of one of the reagents and the stable molecular reagent are slowly flowed. The reaction is then initiated by laser photolysis of the precursor, and the products are detected a short time after the photolysis event. To avoid collisional relaxation of the internal degrees of freedom of the product, the products must be detected in a shorter time when compared to the time between gas-kinetic collisions, that depends inversely upon the total pressure in the cell. In some cases, for example in case of the stable NO product from the H + NO2 reaction discussed in section B2.3.3.2. the products are not removed by collisions with the walls and may have long residence times in the apparatus. Study of such reactions are better carried out with pulsed introduction of the reagents into the cell or under crossed-beam conditions. 

One of the most important characteristics of micelles is their ability to take up all kinds of substances. Binding of these compounds to micelles is generally driven by hydrophobic and electrostatic interactions. The dynamics of solubilisation into micelles are similar to those observed for entrance and exit of individual surfactant molecules. Their uptake into micelles is close to diffusion controlled, whereas the residence time depends on the sttucture of the molecule and the solubilisate, and is usually in the order of 10 to 10" seconds . Hence, these processes are fast on the NMR time scale. 

In the higher pressure sub-region, which may be extended to relative pressure up to 01 to 0-2, the enhancement of the interaction energy and of the enthalpy of adsorption is relatively small, and the increased adsorption is now the result of a cooperative effect. The nature of this secondary process may be appreciated from the simplified model of a slit in Fig. 4.33. Once a monolayer has been formed on the walls, then if molecules (1) and (2) happen to condense opposite one another, the probability that (3) will condense is increased. The increased residence time of (1), (2) and (3) will promote the condensation of (4) and of still further molecules. Because of the cooperative nature of the mechanism, the separate stages occur in such rapid succession that in effect they constitute a single process. The model is necessarily very crude and the details for any particular pore will depend on the pore geometry. 

The following data for a 2 factorial design were collected during a study of the effect of temperature, pressure, and residence time on the %yield of a reaction. " ... 

Results obtained for two mixed plastics are summarized in Table 4. A balance exists between process temperature, plastics feed rate, and product yields (67). For example, lower temperatures increase wax formation due to incomplete depolymerization. Slower feed rates and increased residence times reduce wax formation and increase the yield of Hquids. The data summarized in Table 4 illustrate that the addition of PET to a HDPE PP PS mixture changes the performance of the Conrad process. Compared to the reference HDPE PP PS mixture, increased amounts of soHds ate formed. These are 95% terephthahc acid and 5% mono- and bis-hydroxyethyl esters. At higher temperatures, apparentiy enough water remains to promote decarboxylation. 

In this condenser, part of the stripper off-gases are condensed (the heat of condensation is used to generate low pressure steam). The carbamate formed and noncondensed NH and CO2 are put into the reactor bottom and conversion of the carbamate into urea takes place. The reactor is sized to allow enough residence time for the reaction to approach equiUbrium. The heat required for the urea reaction and for heating the solution is suppHed by additional condensation of NH and CO2. The reactor which is lined with 316 L stainless steel, contains sieve trays to provide good contact between the gas and Hquid phases and to prevent back-mixing. The stripper tubes are 25-22-2 stainless steel. Some strippers are still in service after almost 30 years of operation. 

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