Jens Hagen (WILEY-VCH Industrial Catalysis A Practical Approach Second, Completely Revised and Extended Edition4 Catalysis Reactors The selection and design of a catalysis reactor depends on the type of process and fundamental process variables such as residence time, temperature, pressure, mass transfer between different phases, the properties of the reactants, and the available catalysts [16] The prerequisites for successful reactor design ate the coupling of the actual microki- netics of the reaction with the mass and energy transfer and the determination of fluid~ dynamic influences such as backmixing, residence time distribution, ete. The factors that influence the modeling of a reactor are summarized in Figure 14-1 [11]. The choice and calculation of the reactor for a specific chemical reaction involves solving the following problems, on the basis of theoretical knowledge or by more empirical considerations = Choice of the reactor type according to the flow behavior of the fluid — Heat removal Process conditions Operating mode: Nature of reactants, continuous, conversion, product semicontinuous, distribution batch Hydrodynamics: ireulation of the Thermodynamics Siferent phases, back- mixing residence time distibution [Reaction kinetin] Mass and heat tranetor Morphological and ‘mechanical properties of the catalyst ~ ig. 14-1 Influences on the design of catalysis reactors, Industrial Catalysis: A Practical Approach, Second alton Jens Hagen Copyright © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3.527-311440 403a0 14 Catalysis Reactors w1 Two-Phase Reactors (13, 15] Gas-phase reactions in the presence of solid catalysts have numerous technical ad- vantages. They can generally be carried out continuously at low to medium pressure. In comparison to liquid-phase processes, they usually require higher reaction tem- peratures and therefore thermally stable starting materials, products, and catalysts. For this reason, the selectivity of gas-phase processes is often lower than that of li- quid-phase processes, Of major importance in this type of reaction is a large surface area of the solid. Depending on the nature of the solid (particle size, porosity, etc.), the required resi- dence time, the mass-flow mode, and the heat transfer, a wide range of different re- actors are used (Fig. 14-5). ‘The most important factors to be considered in the design of such reactors are: 1) Residence-time distribution: influence on conversion and selectivity. 2) Temperature control: maintenance of temperature limits, axially and radially; minimum temperature difference between reaction medium and catalyst surface, as well as within the catalyst particle. 3) Catalyst lifetime and catalyst regeneration. 4) Pressure drop as a function of catalyst shape and gas velocity. The most widely used types of reactor for heterogeneously catalyzed reactions in the chemical and petrochemical industries are fixed-bed and fluidized-bed reactors [726]. The most important reactors for heterogeneously catalyzed reactions are the fixed-bed reactors, They can be classified according to the manner in which the temperature is controlled into reactors with adiabatic reaction control, reactors with autothermal reaction control, and those with reaction control by removal or supply of heat in the reactor. Some of the well-known reactor designs are discussed below. Single-Bed Reactor The single-bed reactor is the simplest catalysis reactor. It is completely filled with catalyst and is mainly used for thermally neutral and autothermal gas reactions. Owing to its design, the pressure drop is high, and the residence-time distribution has a major influence on the selectivity and conversion of the reaction. Of particular importance is the maintenance of temperature limits, both axially and radially, as heat.removal is naturally poor. An advantage is the ease of catalyst regeneration. Process Examples ~ Isomerization of light gasoline: 400-500°C, 20-40 bar Hy pressure, PUAlOs catalyst. ~ Catalytic reforming of solvent naphtha: cascade of 3-5 single-bed reactors, 450— 550°C, 20-25 bar Hz pressure, Cry03/Al03/K30 catalyst — Hydrocracking of heavy hydrocarbons: 400-500 °C, 20-60 bar Hy pressure, oxi- die or sulfidic hydrogenation catalysts (Mo/W, Co/W) on acidic supports.14.1 Two-Phase Reactors | 411 HTM se Heat 0 exchangers bed a s I Single-bed Mutibed Muttubutar reactor reactor reactor Solid Particles Shallow-bed Fluidized-bed reactor reactor Fig. 145 Examples of important gas-solid reactors [126] Multibed Reactor ‘This type of reactor contains several separate, adiabatically operated catalyst beds, allowing defined temperature control. Several methods of cooling are possible: in- ternal or external heat exchangers or direct cooling by introduction of cold gas (quench reactor). The multibed reactor is particularly suitable for high production capacities, Process Examples. — Ammonia synthesis: several adiabatically operated catalyst layers with interstage cooling, 400-500°C, 200-300 bar, iron oxide catalyst. — Methanol synthesis by the high-pressure process: CO/Hz, 350-400°C, 200— 300 bar, Zn/Cr oxide catalyst, quench reactor. — Contact process: oxidation of SO, to SO3, 450-500°C, V.Os catalyst, external heat exchanger.2 14 Catalysis Reoctors Multitubular Reactors In these reactors the catalyst is located in a bundle of thin tubes (diameter: 1.5— 6 cm), around which the heat-transfer medium (boiling liquid, high-pressure water, salt melt) flows, giving intensive heat exchange. Multitubular reactors with up to 20000 or more parallel tubes are used preferentially for strongly endo- or exother- mic reactions. The high flow rate in the tubes leads to a relatively uniform residence time, so that the reactors can be modeled as almost ideal tubes. Due to the nonadia- batic process control, a characteristic axial temperature gradient becomes estab- lished. The radial temperature profile in the catalyst bed must also be taken into ac~ count, Owing to the design of the reactor, changing the catalyst is a laborious pro- cess that can be carried out at most twice per year. Process Examples — Low-pressure methanol synthesis: 260-280°C, 45~55 bar, Cu/ZnO catalysts. — Oxidation of ethylene to ethylene oxide: 200~250°C, supported silver catalyst. — Hydrogenation of benzene to cyclohexane: 250°C, 35 bar Hy, Ni catalysts. — Dehydrogenation of ethylbenzene to styrene: 500-600°C, endothermic, FesOs catalyst. Shallow-Bed Reactors In these reactors the catalyst is present in the reactor in the form of a thin packed bed or metal net. They are used for reactions with very short residence times and mostly for autothermally operated, heterogeneously catalyzed gas reactions at high temperatures. Process Examples: ~ Dehydrogenation of methanol to formaldehyde: methanol, air and steam are passed over a 5—10 cm high bed of silver crystals. — Combustion of ammonia to form nitrous gases (Ostwald nitric acid process): cold air and ammonia are introduced, with an excess of air such that the heat of reac- tion is consumed in heating the initial mixture; 900°C, PURh nets ~ Ammoxidation of methane (Andrussow process for the production of HCN): ‘methane, ammonia, and air are passed over a Pt or PURh net at 800-1000°C. Fluidized-Bed Reactors In a fluidized-bed reactor, finely divided catalyst particles of diameter 0.01-1 mm are held in suspension by flowing gas. This widely used technique allows large vo- lumes of solid to be handled in a continuous process. The factors for the formation of the fluidized state are the gas velocity and the diameter of the particles, Large- scale industrial reactors are operated with fine-grained catalysts and high gas veloci- ties to give a large solid-gas exchange area and high throughput.14.2 Three-Phose Reactors The thorough mixing of the solid leads to effective gas-solid heat exchange with an excellent heat-transfer characteristic and hence a uniform temperature distribution in the reaction space. Heat-transfer coefficients are typically 100-400 kJm~?h~'K~! and for small particles can be as high as 800 kIm~*h~'K~", For fine particles and at high reaction rates, circulating fluidized-bed reactors with separation and recycling of the solid are particularly suitable. To give a conversion comparable to that of a fixed-bed reactor, a fluidized-bed re- actor must be considerably larger. Disadvantages are the broad residence-time distri- bution of the gas, which favors side reactions; attrition of the catalyst particles; and the difficult scale-up and modeling of this type of reactor. Process Examples — Ammoxidation of propene to acrylonitrile (SOHIO process): a mixture of propene, ammonia, and air reacts on a Bi/Mo oxide catalyst; 400~-S00°C, 0.3~2 bar, high gas throughput, small catalyst particles (mean particle diameter ca. 50 jim); the high heat of reaction is removed by cooling coils incorporated in the fluidized bed, — Oxidation of naphthalene or o-xylene to phthalic anhydride: The liquid starting ‘material is injected into the fluidized bed, which has a temperature of 350- 380°C; large excess of air, V20,/silica gel catalyst, low gas throughput, catalyst particle diameter of up to 300 pum. ~ Catalytic cracking of kerosene or vacuum distillate to produce gasoline: capaci- ties up to 3 x 10° tla, 450-550°C, aluminosilicate catalysts. 14.2 Three-Phase Reactors (7, 12] The reaction of gases, liquids, and dissolved reactants on solid catalysts requires in- tensive mixing to ensure fast mass transfer from the gas phase to the liquid phase and from the liquid phase to the catalyst surface. Three-phase reactions between gascous and liquid reactants and solid catalysts are often encountered in industrial chemistry. Figure 14-6 shows a stirred-tank-reactor cascade for the development of catalytic processes. A well-known example is the hydrogenation of a liquid on a noble metal catalyst. Conducting the process in the liquid phase has advantages and disadvantages, which we will briefly discuss. ‘The generally low reaction temperatures allow the production of heat-sensitive compounds and the use of thermally less stable but particularly active or selective catalysts such as: ~ Solid-tiquid phase (SLP) catalysts — Ton-exchange catalysts, — Immobilized transition metal complex catalysts Liquid-phase processes generally give higher space-time yields than gas-phase processes. The higher heat capacity and thermal conductivity of liquids leads to bet- a3al 14 Catalysis Reactors Fig. 14-6 Miniplant unit for the development of catalytical processes in three-phase reactions (Degussa AG, Marl, Germany) ter heat transfer in the catalyst layer and in the heat exchangers. Heat can be re- moved very effectively by evaporative cooling. With liquids, the reactivity can be in- fluenced by, for example, suppressing secondary reactions in the liquid phase and by modification of the active centers of the catalyst. Disadvantages of liquid-phase processes are ~ Separation and purification of the product streams is laborious ~ Separation of suspended catalyst from the reaction products is often difficult ~ Mass transfer is hindered by the liquid phase, and the necessary intensive mixing Of the material streams requires mechanically stable catalysts and supports and of- ten high pressures Depending on the arrangement of the catalyst, three-phase reactors can be classsi- fied as: ~ Fixed-bed reactors with a stationary catalyst packing ~ Suspension reactors, in which the catalyst is finely dispersed in the liquid (Fig. 14-7) 142.1 Fixed-Bed Reactors Fixed-bed reactors contain a bed of catalyst pellets (diameter 3-50 mm). The cata lyst lifetime in these reactors is greater than three months. The best known design is the trickle-bed reactor (8, 10] Ina trickle-bed reactor the liquid flows downwards through a packed catalyst bed, while the gas can flow cocurrently or countercurrently to the liquid. The gas phase, which is present in excess, is the continuous phase. In the cocurrent trickle-bed re- actor (Fig. 14-8), the gas/liquid mixture leaving the bottom of the reactor is sepa-14.2 Three-Phase Reactors [es ——4L 8 ® o.— —+s Ls ° Ls suspersin eater as Suspensonacor —_The-vodeacr Sorinnunorouthsivedink — eotusbecolm (eon) (continuous) Fig. 14-7 Three-phase reactors Fig. 148 Pilot plant with 0.2 L trickle-bed reactor (Hoffmann-La Roche, Kaiseraugst, Switzerland)a6 14 Catalysis Reactors rated, and the gas is recycled. The advantages of this type of reactor are the good re- sidence-time behavior of the liquid and gas streams and the possiblity of operating with high liquid flows. In the simplest case the flow of the liquid phase can be des- ribed as plug flow (ideal tube). Backmixing is not a problem provided the catalyst bed is sufficiently long (at least 1 m), Average values for the liquid flow are 10-30 m’m~h~', and for the gas flow 300-1000 m’m~?h™', Solidliquid separation is not necessary. Disadvantages are the poor heat removal and the occurrence of hot spots with potential instabilities, However, since the reactors are generally operated adiabatically, the relatively poor heat removal is not necessarily a problem. Stream formation in large-diameter reactors and wall channeling in small-dia- Meter reactors can lower reactor performance. Often the catalyst is not fully exploited owing to incomplete wetting by the liquid and low mass-transfer rates to- gether with low residence times within the catalyst pellets, Trickle-bed reactors are widely used in petrochemical hydrogenation processes and in the production of basic products. They are being used increasingly for the manufacture of fine chemicals. Process Examples (14, 126] ~ Petrochemistry: desulfurization, hydrocracking, refining of cude oil products (€.g., hydrogenative refining of tar fractions from low-temperature carbonization), 300-350 °C, 220 bar, NiS/WS2/Al;03 catalysts), ~ Synthesis of butynediol from acetylene and formaldehyde: reactor height 18 m, diameter 1.5 m, 100°C, 3 bar, copper acetylide catalyst, introduction of cold acet- ylene at various points in the reactor. ~ Selective hydrogenation (cold hydrogenation) of acetylene and allene contained in Cy fractions: up to 50°C, 520 bar, supported Pd catalysts ~ Hydrogenation of aldehydes and Ketones to alcohols: 100~150°C Ni, Pa, Pt catalysts. ~ Hydrogenation of butynediol, adiponitile, and fatty acid esters. ~ Reduction of adiponitrile to hexamethylenediamine: 100-200°C, 200-400 bat, Co of Ni on AO, ~ Fine chemicals: hydrogenation of quinones, sugars, lactones, substituted aromatic compounds. up to 30 bar, Small trickle-bed reactors, operated in batch mode by recycling the liquid phase, are also used, for example, for the hydrogenation of trifluoroacetic acid [11]. 142.2 Suspension Reactors (2, 4 In suspension reactors, gas and catalyst particles are distributed in a relatively large volume of liquid. Catalyst concentrations are typically less than 3 % with particle sizes of less than 0.2 mm. In general, the reactants (L and G) are introduced into the lower part of the reactor together with the catalyst (S), which is suspended in the14.2 Three-Phase Reactors liquid. In the upper part of the reactor, the unconsumed gas is separated or removed together with the liquid product (L) and the suspended catalyst (S). In this system, the liquid is the continuous phase, in which the gas is dispersed as bubbles. Suspen- sion reactors behave largely as gas-liquid systems, and little energy is required for suspension. Suspension reactors can be regarded as isothermal with a behavior that approxi- ‘mates that of an ideal stirted tank. The reactors are followed by a phase-separation unit in which the liquid is separated from the catalyst and the gas. The gas and the catalyst can be partially recycled. The advantage of suspension reactors is the effective exploitation of the catalyst, which is completely wetted by the liquid. Because of the small particle size, diffu- sion processes within the catalyst play no role, and owing to the good temperature control, local overheating can not occur. This type of reactor is particularly suitable for rapidly deactivated catalysts since rapid catalyst replacement is possible. Disadvantages are potential problems in separating the catalyst and the risk of fractionation and sedimentation of the catalyst in the reactor. Since the residence- time behavior is similar to that of a continuous ideal stirred tank, lower conversions are attained compared to a fixed-bed reactor. A comparison of the two most impor- tant three-phase reactors — the trickle-bed reactor and the suspension reactor — is given in Table 14-1 The majority of suspension reactors are stirred tanks and bubble columns (see Fig. 14-7). Other industrially important variants of the suspension reactor are the loop and Buss (jet) loop reactors, which achieve better exploitation of the catalyst by recirculating it in a loop (Fig. 14-9) Three-phase bubble columns are operated with the liquid flowing cocurrently with the rising gas. They are used when the mass-transfer resistance lies on the liquid side and the reaction is relatively slow. The gas is introduced at the bottom of the re- actor through perforated plates or sintered disks, and the reactors often incorporate sieve trays. Without internals the liquid is almost ideally mixed at high gas veloci- ties, and this results in good heat transfer. The residence-time distribution of the gas and the liquid corresponds approximately to that of a cascade of stirred-tank reac- tors. The advantages of bubble columns are the simple, inexpensive design and their versatility. Reaction volumes of up to several cubic meters are possible. Bubble col- ‘umas with internal circulation are also used (loop and air-lift reactors). In loop reactors, the liquid is completely mixed in a relatively small reactor, which gives good heat removal, In the Buss loop reactor, the liquid with the suspended catalyst form a jet that en- trains the gas, finely dividing it. The high flow rates lead to intensive turbulence and a high interfacial area between the small gas bubbles and the suspension. An ex- ‘ternal heat exchanger in the loop allows isothermal operation and very effective re~ moval of the heat of reaction from the system, even with highly exothermic reac- tions. However, Buss loop reactors can only be operated in a discontinuous mode and require special, highly abrasion resistant catalysts. a7ag 14 Catalysis Reactors Table 14-1 Comparison of trickle-bed and suspension reactors Characteristic Trickle-bed reactor ‘Suspension reactor Process mode continuous mostly batch Degree of automation high low Conditions moderate mild (temperature, pressure) ‘Temperature depends on position uniform Pressure drop high ow Reactor performance high moderate Plant size casily extended by limited tube bundles Selectivity ow high Liquid content low high Residence time behavior ~ liquid ideal plug flow reactor ideal stirred tank ~ plug flow reactor with axial dispersion ~ gas ideal plug flow reactor plug flow reactor with axial dispersion Catalyst very low cal effectiveness factor Catalyst performance low high Heat usage unfavorable favorable Applicability limited universal (selectivity) Particular suitability high liquid feeds in case of rapid catalyst deactivation Process Examples: ~ Liquid-phase hydrogenation of chlorinated aromatic nitro compounds; for exam- ple, conversion of p-chloronitrobenzene to p-chloroaniline in a stirred tank with a powder catalyst (Ni/SiO2 or Pd on activated carbon). — Continous hydrogenation of fats in a chamber reactor (several stirred chambers one above the other), narrow residence-time spectrum is an advantage, 150 200°C, 5-15 bar. ~ Hydrogenation of benzene to cyclohexane in a bubble column: 200-225°C, ca. 50 bar, Raney nickel (10-100 um), removal of heat of reaction from the suspen- sion in an external circuit. Cyclohexane is removed as a gas. — Hydrogenation of fatty esters to fatty alcohols in a bubble column. ~ Hydrogenation of fats and fatty acids in a tank reactor with a turbine stirrer (110-120 rpm); Hy is introduced through a distributor at the bottom, 150— 200°C, up to 30 bar, Ni/Cu catalysts.142 Three-Phase Reactors | 419 Loop reactors with external internal Buss (je) loop reactor circulation Fig. 149 Variants ofthe suspension reactor — Hydrogenation of oil in a Buss loop reactor. — Hydrogenation of 2-ethylanthraquinone to 2-ethylanthraquinol: bubble column with parallel chambers, suspended catalyst. The choice of the “right” reactor for a given catalytic reaction can often not be answered mambiguously, as shown, for example, by the fact that different technolo- gies compete in the high-pressure hydrogenation of adiponitrile in the presence of ammonia (Table 14-2) [11] In new plants for the hydrogenation of fine chemicals there is currently a trend to use Buss loop reactors rather than conventional stirred tanks, Today, trickle-bed re- actors are generally preferred to suspension reactors for hydrogenation processes. Table 142 Various technologies for the hydrogenation of adiponitrile [17] Company Reactor Temperature control BASF trickle bed cooling and partial recycling of liquid phase Phillips suspension loop reactor DuPont sump reactor (Liquid and gas are several catalyst beds with intermediate passed cocurrent from below into cooling catalyst fixed bed) Ic fixed bed cooling of recycled off-gas Vickers multitubular reactor with downward evaporative cooling with inert solvents, Zimmer —_cocurrent operation20 14 Catalysis Reactors The examples of the hydrogenation of glucose to sorbitol and of esters to alcohols demonstrate the dilemma of reactor choice. Formerly, suspension reactors with Raney nickel or copper chromite catalysts were used, but today trickle-bed reactors with novel noble metal catalysts are preferred. The following advantages are claimed for the trickle-bed reactors: ~ No loss of metal; higher product quality (no contamination) ~ Fewer side reactions in the liquid phase due to the lower liquid holdup The major disadvantage is the risk of poor temperature control owing to the oc- currence of hot spots in the catalyst bed. Examples of this are: ~ Benzene is formed as a side product in the hydrogenation of cyclohexene ~ In the hydrogenation of benzoic acid, decarboxylation of the cyclohexane car- boxylic acid product can occur, Therefore, a cascade of stirred-tank reactors is preferred here The catalyst form is is also decisively influenced by the chosen reactor type. It has been found experimentally that at particle sizes below 0.1 mm pore diffusion is rarely limiting, whereas at particle sizes above 5 mm, pore diffusion is always domi- nant. This is the reason why shell catalysts are advantageously used in trickle-bed reactors. The diffusion limitation need not always result from the tansport of the gas in the pores; it can also be due to the substrate, Such effects are found with long-chain organic molecules, for example: ~ Hydrogenation of linoleic esters (Cs): a shell catalyst with Pd on activated car- bon is recommended ~ Hydrogenation of C1-Cz nitriles: a large-pore catalyst based on Ni/MgO/SiO, is recommended [11] These few examples show how the complexity of three-phase processes greatly complicate reactor modeling and scale-up. The engineer responsible for reactor de- sign must be familiar with reaction engineering and should also work in close coop- eration with the synthetic chemist and the catalyst expert. 143 Reactors for Homogeneously Catalyzed Reactions [3, 5] Homogeneously catalyzed reactions with dissolved transition metal complexes are generally carried out in the usual two-phase reactors for gas-liquid systems. The standard reactor is the batch or continuous stirred tank. Since diffusion problems are rarely encountered in homogeneous catalysis, the reaction engineering is much sim- pler than for heterogeneously catalyzed reactions. Efficient mixing of the two phases is important as this determines the exchange surface area between the gas and the liquid. Modern stirred tanks (Fig, 14-10) are often equipped with gasifying stirers, in which the gas is drawn in at the top of the drive shaft and then finely dispersed by the stirrer blades.14.3 Reactors for Homogeneously Cotalyzed Reactions | 421 Fig. 14-10 0.5 L stirred autoclave reactor in a high-pressure cell (FH Mannheim, Germany) ‘Since we have already become familiar with the most important reactors for gas— liquid reactions, we will restrict ourselves here to a few examples of processes in special reactors, Bubble-column Reactors. — Homogeneously catalyzed air oxidation of hydrocarbons (¢.g., of toluene to ben- zoic acid): 130-150°C, 1-10 bar, Mn or Co salts as catalyst, ~ Oxidation of p-xylene to terephthalic acid with Co/Mn salts and bromide at 100— 180°C and 1-10 bar, — Oxidation of ethylene to acetaldehyde (Wacker process): 100-120°C, 1-10 bar, PACly/CuCl, catalyst. — Oxo synthesis: reaction of ethylene with synthesis gas to form propanal, 100- 150°C, 200-300 bar, propanol solvent, [HCo(CO),] catalyst. Loop Reactors. ~ Oxo synthesis. ~ Carbonylation of methanol with CO to produce acetic acid, 150°C, 200-300 bar, Col, catalyst (Rh catalysts preferred nowadays).am 14 Catalysis Reactors Stirred Tanks ~ Hydroformylation of olefins with Co or Rh catalysts, ~ Low-pressure hydroformylation of propene to butanals with water-soluble Rh Phosphine complexes (Rhéne-Poulene/Ruhrchemie process): 50-150°C, 10— 100 bar, 10-100 ppm Rh, ~ Polymerization of ethylene with TiCl4/AI(C2Hs)3 at 70-160°C and 2-25 bar. > Exercises for Chapter 14 Exercise 141 The design equation for a catalysis reactor is: Xy ren _ f tn Fino ret ) To which quantity is the left side of the equation proportional? b) Prepare a graphical depiction of the integral ©) To which ideal reactor does the catalysis reactor correspond? 4) What is meant by the term effective reaction rate? Exercise 14.2 The driving force of a reaction is much smaller in a reactor with backmixing than in 4 reactor without backmixing. Why? Exercise 14.3, The kinetics of a second-order heterogeneously catalyzed gas-phase reaction of the type A->R is investigated in a differential circulating reactor. Under isothermal conditions with a reactor feed stream of y= 1 L/h and ca.y = 2 moV/L and a cata- lyst quantity of 3 g, an outlet concentration of ca = 0.5 mol/L was obtained. a) Calculate the rate constant for the reaction, +») What quantity of catalyst would be required in an integral reactor (ideal plug flow Feactor), in which a conversion of 80% is to be achieved for a feed stream of 1000 Lin with a concentration of c4,9=1 mol/L? ©) The same reaction is carried out in a reactor with complete backmixing. What quantity of catalyst is required (conditions as in b). Discuss the result.