Reactor productivity

For the assessment of reactor productivity that is independent of catalyst, the space-time yield (s.t.y.) [Eq. (2.29)]. is considered, as in any chemical process. 

An increase in s.t.y. in the same reactor is equivalent to an increase in reaction rate. When considering the Michaelis-Menten equation [Eq. (2.3) v = vmax[S]/(fCM + [S]) = k J l, [S]/(I M + [S])], there are three possible ways to achieve a maximum reaction rate  

High substrate concentration (increase of space-yield). Enzyme reactions can be accelerated by increasing the substrate concentration up to the limit of saturation (= 10Km). If [S] fCM, the enzyme is saturated and Eq. (2.3) is reduced to Eq. (2.30). 

At substrate saturation, the reaction is zeroth-order with respect to substrate. With a loosely binding substrate, i.e., a high KM value, the enzyme is often saturated only above the solubility limit of the substrate. To improve the reaction rate or the s.t.y. further, according to Eq. (2.29) the yield per unit time must be increased, which means enhancing either the biocatalyst concentration and/ or the time constant kcat. 

High enzyme concentration. The reaction rate and s.t.y. can be enhanced by increasing the catalyst concentration [E] in practice, however, in contrast to the formalism of Eq. (2.3), owing to an either excessive viscosity increase or excess of deactivated protein in the reactor, a maximum limit of enzyme concentration is reached. 

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The reactor products are so hot or corrosive that if passed directly to a heat exchanger, special materials-of-construction or an expensive mechanical design would be required. 

The reactor product cooling would cause excessive fouling in a conventional exchanger. 

The liquid used for the direct heat transfer should be chosen such that it can be separated easily from the reactor product and so recycled with the minimum expense. Use of extraneous materials, i.e., materials that do not already exist in the process, should be avoided because it is often difficult to separate and recycle them with high efficiency. Extraneous material not recycled becomes an effluent problem. As we shall discuss later, the best way to deal with effluent problems is not to create them in the first place. 

Heat transfer. Once the basic reactor type and conditions have been chosen, heat transfer can be a major problem. Figure 2.11 summarizes the basic decisions which must be made regarding heat transfer. If the reactor product is to be cooled by direct contact with a cold fluid, then use of extraneous materials should be avoided. 

Some small amount of byproduct formation occurs. The principal byproduct is di-isopropyl ether. The reactor product is cooled, and a phase separation of the resulting vapor-liquid mixture produces a vapor containing predominantly propylene and propane and a liquid containing predominantly the other components. Unreacted propylene is recycled to the reactor, and a purge prevents the buildup of propane. The first distillation in Fig. 10.3a (column Cl) removes... 

In addition to the indirect cooling/heating within the reactor, the reactor feed is an additional cold stream and the reactor product an additional hot stream. 

The reactor effluent might require cooling by direct heat transfer because the reaction needs to be stopped quickly, or a conventional exchanger would foul, or the reactor products are too hot or corrosive to pass to a conventional heat exchanger. The reactor product is mixed with a liquid that can be recycled, cooled product, or an inert material such as water. The liquid vaporizes partially or totally and cools the reactor effluent. Here, the reactor Teed is a cold stream, and the vapor and any liquid from the quench are hot streams. 

The gaseous reactor product is cooled first by boiler feedwater before entering a cooling water condenser. The cooling duty provided by the boiler... 

A typical flow diagram for pentaerythritol production is shown in Figure 2. The main concern in mixing is to avoid loss of temperature control in this exothermic reaction, which can lead to excessive by-product formation and/or reduced yields of pentaerythritol (55,58,59). The reaction time depends on the reaction temperature and may vary from about 0.5 to 4 h at final temperatures of about 65 and 35°C, respectively. The reactor product, neutralized with acetic or formic acid, is then stripped of excess formaldehyde and water to produce a highly concentrated solution of pentaerythritol reaction products. This is then cooled under carefully controlled crystallization conditions so that the crystals can be readily separated from the Hquors by subsequent filtration. 

Suspension polymerization of VDE in water are batch processes in autoclaves designed to limit scale formation (91). Most systems operate from 30 to 100°C and are initiated with monomer-soluble organic free-radical initiators such as diisopropyl peroxydicarbonate (92—96), tert-huty peroxypivalate (97), or / fZ-amyl peroxypivalate (98). Usually water-soluble polymers, eg, cellulose derivatives or poly(vinyl alcohol), are used as suspending agents to reduce coalescence of polymer particles. Organic solvents that may act as a reaction accelerator or chain-transfer agent are often employed. The reactor product is a slurry of suspended polymer particles, usually spheres of 30—100 pm in diameter they are separated from the water phase thoroughly washed and dried. Size and internal stmcture of beads, ie, porosity, and dispersant residues affect how the resin performs in appHcations. 

Economic evaluations of algal production indicate that production costs vary from 0.15 to 4.00/kg of algal product, depending on type of bioreactor, culture technique, and operating conditions (51). For systems with controlled agitation and carbonation, including raceways and tubular reactors, production costs ate estimated to range from 2.00 to 4.00/kg. 

Hot product char carries heat into the entrained bed to obtain the high heat-transfer rates required. Feed coal must be dried and pulverized. A portion of the char recovered from the reactor product stream is cooled and discharged as product. The remainder is reheated to 650—870°C in a char heater blown with air. Gases from the reactor are cooled and scmbbed free of product tar. Hydrogen sulfide is removed from the gas, and a portion is recycled to serve as the entrainment medium. 

The final composition of the reactor product gas is estabUshed by the water gas shift equiUbrium at the reactor outiet waste-heat exchanger inlet where rapid cooling begins. Some units quench instead of going directiy to heat exchanger. 

Equipment. Partial-oxidation gasification section equipment in many plants consists essentially of (/) the gasification reactor (2) the waste-heat exchanger for heat recovery from the hot reactor gas or direct quench system (J) the economizer heat exchanger for further heat recovery (4) the carbon removal system for separating carbon from the reactor product gas and (5) the carbon recovery system for recycle of carbon. 

The Tokuyama Soda single-step catalyst consists of a zirconium phosphate catalyst loaded with 0.1—0.5 wt % paHadium (93—97). Pilot-plant data report (93) that at 140°C, 3 MPa, and a H2 acetone mole ratio of 0.2, the MIBK selectivity is 95% at an acetone conversion of 30%. The reactor product does not contain light methyl substituted methyl pentanes, and allows MIBK recovery in a three-column train with a phase separator between the first and second columns. 

Some alkylphenol appHcations can tolerate "as is" reactor products, most significantly in the production of alkylphenol—formaldehyde resins. These resins can tolerate some of the reactant and by-product from the alkylphenol reactor because they undergo purification steps. This resin production route has both capital and operating cost advantages over using purer alkylphenol streams as feedstock. For these savings, the resin producer must operate the process in such a way as to tolerate a more widely varying feedstock and assume the burden of waste disposal of some unreactive materials from the alkylphenol process. 

Erom 1955—1975, the Ziegler-Natta catalyst (91), which is titanium trichloride used in combination with diethylaluminum chloride, was the catalyst system for propylene polymerization. However, its low activity, which is less than 1000 g polymer/g catalyst in most cases, and low selectivity (ca 90% to isotactic polymer) required polypropylene manufacturers to purify the reactor product by washing out spent catalyst residues and removing unwanted atactic polymer by solvent extraction. These operations added significantly to the cost of pre-1980 polypropylene. 

The H2S comes out with the reactor products, goes through the product-recovery system of the FCCU, and eventually goes to a Claus plant for sulfur recovery. The metal oxide adsorbent recirculates with the spent cracking catalyst back to the regenerator for the next SO adsorption cycle. 

Dichloroethane is produced commercially from hydrogen chloride and vinyl chloride at 20—55°C ia the presence of an aluminum, ferric, or 2iac chloride catalyst (8,9). Selectivity is nearly stoichiometric to 1,1-dichloroethane. Small amounts of 1,1,3-tfichlorobutane may be produced. Unreacted vinyl chloride and HCl exit the top of the reactor, and can be recycled or sent to vent recovery systems. The reactor product contains the Lewis acid catalyst and must be separated before distillation. Spent catalyst may be removed from the reaction mixture by contacting with a hydrocarbon or paraffin oil, which precipitates the metal chloride catalyst iato the oil (10). Other iaert Hquids such as sdoxanes and perfluorohydrocarbons have also been used (11). 

Unreacted 1,1-dichloroethylene exits the reactor as vapor and can be condensed and recycled to the reactor. Product 1,1,1-trichloroethane exits the reactor as a Hquid, along with the Lewis acid catalyst, and can be removed from the catalyst by flash distillation. Selectivity is high however, some dehydrochlorination of the product can occur in the distillation step. 

Because HCl is constandy present in most parts of the equipment, corrosion is always a potential problem. Chlorine and benzene, or any recycled material, must be free of water to trace amounts to prevent corrosion and deactivation of the catalyst. The reactor product contains HCl and iron. In some plants, the product is neutralized with aqueous NaOH before distillation. In others, it is handled in a suitably-designed distillation train, which includes a final residue from which FeCl can be removed with the high boiling tars. 

Table 1. Distributions of Reactor Products from Batch Chlorination of Toluene...

To make the necessary thermodynamic calculations, plausible reaction equations are written and balanced for production of the stated molar flows of all reactor products. Given the heat of reaction for each applicable reaction, the overall heat of reaction can be determined and compared to that claimed. However, often the individual heats of reaction are not all readily available. Those that are not available can be determined from heats of combustion by combining combustion equations in such a way as to obtain the desired reaction equations by difference. It is a worthwhile exercise to verify this basic part of the process. 

RPC Reactor product C PEBL Product E transfeiTed to another plant... 

RPD Reactor product D PBRECY Product B recycle to reactor... 

Flows (columns) FI Cl through F4C3 each create units of REACTL the total flow to the reactor and use up units REACTCP reactor capacity. Flows FlCl through F4C3 create yields of reactor products RPA through RPE. Pure component C is added from an outside source into tank (row) RPC by flow (column) OUTSIDE. 

Figure 3 Schematic spectra of H2O, OH, and atomic O adsorbed on a matai surface illustrate how molecules can be distinguished from their reactor products by fingerprinting.

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