Multitubular

The reaction is exothermic, and multitubular reactors are employed with indirect cooling of the reactor via a heat transfer medium. A number of heat transfer media have been proposed to carry out the reactor cooling, such as hot oil circuits, water, sulfur, mercury, etc. However, the favored heat transfer medium is usually a molten heat transfer salt which is a eutectic mixture of sodium-potassium nitrate-nitrite. 

With a multitubular reactor, conversions of 74—82% per pass can be obtained while generating steam to be used elsewhere in the process (99). 

The highly exothermic nature of the butane-to-maleic anhydride reaction and the principal by-product reactions require substantial heat removal from the reactor. Thus the reaction is carried out in what is effectively a large multitubular heat exchanger which circulates a mixture of 53% potassium nitrate [7757-79-1/, KNO 40% sodium nitrite [7632-00-0], NaN02 and 7% sodium nitrate [7631-99-4], NaNO. Reaction tube diameters are kept at a minimum 25—30 mm in outside diameter to faciUtate heat removal. Reactor tube lengths are between 3 and 6 meters. The exothermic heat of reaction is removed from the salt mixture by the production of steam in an external salt cooler. Reactor temperatures are in the range of 390 to 430°C. Despite the rapid circulation of salt on the shell side of the reactor, catalyst temperatures can be 40 to 60°C higher than the salt temperature. The butane to maleic anhydride reaction typically reaches its maximum efficiency (maximum yield) at about 85% butane conversion. Reported molar yields are typically 50 to 60%. 

Tubular Fixed-Bed Reactors. Bundles of downflow reactor tubes filled with catalyst and surrounded by heat-transfer media are tubular fixed-bed reactors. Such reactors are used most notably in steam reforming and phthaUc anhydride manufacture. Steam reforming is the reaction of light hydrocarbons, preferably natural gas or naphthas, with steam over a nickel-supported catalyst to form synthesis gas, which is primarily and CO with some CO2 and CH. Additional conversion to the primary products can be obtained by iron oxide-catalyzed water gas shift reactions, but these are carried out ia large-diameter, fixed-bed reactors rather than ia small-diameter tubes (65). The physical arrangement of a multitubular steam reformer ia a box-shaped furnace has been described (1). 

Summary of Characteristics of Falling Film Continuous SOj Sulfonation Processes. Both concentric and multitubular reactor systems suppHed by competing manufacturers have surprisingly similar operating characteristics organic feedstock loading of ca 0.4 kg/(h-mm) (circumference) for LAB, and ca 0.3 kg/(h-mm) for alcohol ethoxylates an SO concentration of 3.3—5.0 vol % SO for LAB sulfonation, and 2—3% SO ... 

Process Description. Reactors used in the vapor-phase synthesis of thiophene and aLkylthiophenes are all multitubular, fixed-bed catalytic reactors operating at atmospheric pressure, or up to 10 kPa and with hot-air circulation on the shell, or salt bath heating, maintaining reaction temperatures in the range of 400—500°C. The feedstocks, in the appropriate molar ratio, are vaporized and passed through the catalyst bed. Condensation gives the cmde product mixture noncondensable vapors are vented to the incinerator. 

Separability. One of the greatest advantages of a solid catalyst is that it can be separated easily from the products of reaction. To do this successfully requires careful control of the process conditions so that exposure of the catalyst to nonreactant liquids capable of affecting or dissolving either the catalytic material or the support is prevented or rninimi2ed. Solid catalysts typically are used in axial or radial flow beds and multitubular reactors. Many successful commercial processes maintain the reactants and products in the gas phase while in contact with the catalyst to avoid catalyst degradation problems. 

Catalysts intended for different appHcations may require their own unique types of reactor and operating conditions, but the key to designing a successful system is to use the same feedstock composition that is expected in the ultimate commercial installation and to impose so far as is possible the same operating conditions as will be used commercially (35). This usually means a reactor design involving a tubular or smaH-bed reactor of one type or another that can simulate either commercial multitubular reactors or commercial-size catalyst beds, including radial flow reactors. 

Sasol uses both fixed-bed reactors and transported fluidized-bed reactors to convert synthesis gas to hydrocarbons. The multitubular, water-cooled fixed-bed reactors were designed by Lurgi and Ruhrchemie, whereas the newer fluidized-bed reactors scaled up from a pilot unit by Kellogg are now known as Sasol Synthol reactors. The two reactor types use different iron-based catalysts and give different product distributions. 

Ethylene oxide is produced in large, multitubular reactors cooled by pressurized boiling Hquids, eg, kerosene and water. Up to 100 metric tons of catalyst may be used in a plant. Typical feed stream contains about 30% ethylene, 7—9% oxygen, 5—7% carbon dioxide the balance is diluent plus 2—5 ppmw of a halogenated moderator. Typical reactor temperatures are in the range 230—300°C. Most producers use newer versions of the Shell cesium-promoted silver on alumina catalyst developed in the mid-1970s. 

Oxychlorination of Ethylene to Dichloroethane. Ethylene (qv) is converted to dichloroethane in very high yield in fixed-bed, multitubular reactors and fluid-bed reactors by reaction with oxygen and hydrogen chloride over potassium-promoted copper(II) chloride supported on high surface area, porous alumina (84) ... 

Vinyl chloride is made from ethylene and chlorine with Cu and K chlorides. The Stauffer process employs 3 multitubular reactors in series with 25 mm (0.082 ft) ID tubes (Naworski and Velez, in Leach, ed.. Applied Industrial Catalysis, vol. 1, Academic Press, 1983, p. 251). 

Another process where good temperature control is essential is the synthesis of vinyl chloride by chlorination of ethylene at 200 to 300°C (392 to 572°F), 2 to 10 atm (29.4 to 147 psi), with supported cupric chloride, but a process with multitubular fixed beds is a strong competitor. 

In the process (Figure 7-3), compressed oxygen, ethylene, and recycled gas are fed to a multitubular reactor. The temperature of oxidation... 

Figure 9-4. The Octol Oligomerization process for producing Os s and Ci2 s and Cis s olefins from n-butenes (1) multitubular reactor, (2) debutanizer column, (3) fractionation tower.

So far, consideration has been limited to chemistry physical constraints such as heat transfer may also dictate the way in which reactions are performed. Oxidation reactions are highly exothermic and effectively there are only two types of reactor in which selective oxidation can be achieved on a practical scale multitubular fixed bed reactors with fused salt cooling on the outside of the tubes and fluid bed reactors. Each has its own characteristics and constraints. Multitubular reactors have an effective upper size limit and if a plant is required which is too large to allow the use of a single reactor, two reactors must be used in parallel. 

Subject to resolution of these concerns, scaling in parallel has no obvious limit. Multitubular reactors with 10,000 tubes have been built, e.g., for phthalic anhydride oxidation. 

Cybulski, A., Eigenberger, G., and Stankiewicz, A., Operational and structural nonidealities in modeling and design of multitubular catalytic reactors, Ind. Eng. Chem. Res. 36, 3140-3148 (1997). 

What is needed at this point is a correlation or other means for estimating r] at every point in the reactor. This may be done empirically for example, by running a single tube of what ultimately will be a multitubular reactor. However, some progress has been made in determining r] from first principles. We outline the salient results achieved to date. 

Tube-to-tube interactions. The problems of velocity profile elongation and thermal runaway can be eliminated by using a multitubular reactor with many small-diameter tubes in parallel. Unfortunately, this introduces another form of instability. Tubes may plug with pol5nner that cannot be displaced using the low-viscosity inlet fluid. Imagine a 1000-tube reactor with 999 plugged tubes ... 

Reacting to low conversions avoids most problems. The polyethylene example uses a single, small-diameter tube. This avoids thermal runaway and mitigates the velocity elongation problem. The polystyrene reactor avoids the multitubular stability problem by using a substantially polymerized, high-viscosity feed. 

Mallikarjun, R. and Nauman, E. B., A staged multitubular process for crystal polystyrene, Polym. Process Eng., 4, 31-51 (1986). 

Metal monoliths show good thermal characteristics. A typical support with herringbone channels made from Fecralloy performed satisfactory in automotive applications [27]. Modeling showed that overall heat transfer was about 2 times higher than for conventional pellets [28,29]. Hence, there is potential for structured catalysts for gas-phase catalytic processes in multitubular reactors. 

Two basically different reactor technologies are currently in operation low temperature and high temperature. The former operates at -220 °C and 25-45 bar, employing either a multitubular, fixed bed (i.e. trickle bed) reactor or a slurry bubble column reactor with the catalyst suspended in the liquid hydrocarbon wax product. 

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