Continuous processes reactors

Even though all three reactors share the same precursor delivery system, each tool offers specific advantages. For example, a cold-wall reactor (reactor B) helps prevent decomposition of the precursor before it reaches the substrate. A pulsed aerosol injection system at low pressure (reactor C) allows the film to grow under better-defined conditions than in a continuous process (reactor A) because of the minimization of undesirable transient effects caused by the high volatility of the solvents used.46 A more detailed description of each of the conditions for film growth, including reactor type, precursor type, delivery method, deposition temperature, growth time, and other parameters are summarized in Table 6.2. Depositions were done on bare and Mo-coated... 

An alternative to univariate calibration is to use multivariate techniques to sense when a steady state has been reached in a chemical reaction. This approach has been successfully apphed to the detection of reaction end points [82]. A very similar technique can be used to establish deviation from steady state in a continuous process reactor. 

In general, high-pressure systems can be distinguished as either batch or continuous process reactors. Each type can then be subdivided by their use for chemical reactions or for extraction/fractionation purposes. Continuous reaction processes often consist of a reaction unit followed by an extraction process in order to recover at least one of the reactants. 

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). 

Single-reaction-step processes have been studied. However, higher selectivity is possible by optimizing catalyst composition and reaction conditions for each of these two steps (40,41). This more efficient utilization of raw material has led to two separate oxidation stages in all commercial faciUties. A two-step continuous process without isolation of the intermediate acrolein was first described by the Toyo Soda Company (42). A mixture of propylene, air, and steam is converted to acrolein in the first reactor. The effluent from the first reactor is then passed directiy to the second reactor where the acrolein is oxidized to acryUc acid. The products are absorbed in water to give about 30—60% aqueous acryUc acid in about 80—85% yield based on propylene. 

Iodine Pentafluoride. Iodine pentafluoride is produced by the reaction of iodine and fluorine. Because iodine has a high melting poiat, the reaction is either performed ia a solvent or the reaction is maintained at a temperature where the iodine is Hquid. In a continuous process usiug a solvent (104), ca 1% I2 is dissolved iu IF and passed to a reactor where it is contacted with F2 gas. The IF is continuously discharged from the reactor where a small portion is taken off as product and the larger portion of the stream is recycled. 

The process options reflect the broad range of compositions and gas volumes that must be processed. Both batch processes and continuous processes are used. Batch processes are used when the daily production of sulfur is small and of the order of 10 kg. When the daily sulfur production is higher, of the order of 45 kg, continuous processes are usually more economical. Using batch processes, regeneration of the absorbant or adsorbant is carried out in the primary reactor. Using continuous processes, absorption of the acid gases occurs in one vessel and acid gas recovery and solvent regeneration occur in a separate reactor. 

The polymerization of monomers to form hydrocarbon resins is typically carried out by either the direct addition of catalyst to a hydrocarbon fraction or by the addition of feed to a solvent—catalyst slurry or solution. Most commercial manufacturers use a continuous polymerization process as opposed to a batch process. Reactor temperatures are typically in the range of 0—120°C. 

Reaction times can be as short as 10 minutes in a continuous flow reactor (1). In a typical batch cycle, the slurry is heated to the reaction temperature and held for up to 24 hours, although hold times can be less than an hour for many processes. After reaction is complete, the material is cooled, either by batch cooling or by pumping the product slurry through a double-pipe heat exchanger. Once the temperature is reduced below approximately 100°C, the slurry can be released through a pressure letdown system to ambient pressure. The product is then recovered by filtration (qv). A series of wash steps may be required to remove any salts that are formed as by-products. The clean filter cake is then dried in a tray or tunnel dryer or reslurried with water and spray dried. 

Many methods for the conversion of acid copolymers to ionomers have been described by Du Pont (27,28). The chemistry involved is simple when cations such as sodium or potassium are involved, but conditions must be controlled to obtain uniform products. Solutions of sodium hydroxide or methoxide can be fed to the acid copolymer melt, using a high shear device such as a two-roU mill to achieve uniformity. AH volatile by-products are easily removed during the conversion, which is mn at about 150°C. A continuous process has been described, using two extmders, the first designed to plasticate the feed polymer and mix it rapidly with the metal compound, eg, zinc oxide, at 160°C (28). Acetic acid is pumped into the melt to function as an activator. Volatiles are removed in an extraction-extmder which follows the reactor-extmder, and the anhydrous melt emerges through a die-plate as strands which are cut into pellets. 

Shell Higher Olefins Process (SHOP). In the Shell ethylene oligomerization process (7), a nickel ligand catalyst is dissolved in a solvent such as 1,4-butanediol (Eig. 4). Ethylene is oligomerized on the catalyst to form a-olefins. Because a-olefins have low solubiUty in the solvent, they form a second Hquid phase. Once formed, olefins can have Htfle further reaction because most of them are no longer in contact with the catalyst. Three continuously stirred reactors operate at ca 120°C and ca 14 MPa (140 atm). Reactor conditions and catalyst addition rates allow Shell to vary the carbon distribution. 

Solution Polymerization. In this process an inert solvent is added to the reaction mass. The solvent adds its heat capacity and reduces the viscosity, faciUtating convective heat transfer. The solvent can also be refluxed to remove heat. On the other hand, the solvent wastes reactor space and reduces both rate and molecular weight as compared to bulk polymerisation. Additional technology is needed to separate the polymer product and to recover and store the solvent. Both batch and continuous processes are used. 

Trioctylamine has been prepared, in a continuous process, using 5,200 kg of -octanol, 100 kg of copper formate catalyst, 500 kg of -octylamine, 10 kg of calcium hydroxide, and 240 kg of ammonia (58). Ammonia was added over a 10-h period while 10 m of hydrogen/h was passed through the reactor at a reaction temperature of 180—200°C. The final product was composed of 94% trioctylamine, 2% dioctylamine, 1% octylamine, and 0.5% -octanol. A... 

Another nickel cataly2ed process is described ia a Tolochimie patent (28). Reaction conditions claimed are 1—2.4 MPa (150—350 psi) at 100°C minimum. The combination continuous stirred reactor and gravity decanter uses density-driven circulation between the two vessels to recirculate the catalyst to the reaction 2one without the use of filters or pumps. Yield and catalyst usage can be controlled by varying the feed rates. 

Batch reactors often are used to develop continuous processes because of their suitabiUty and convenient use in laboratory experimentation. Industrial practice generally favors processing continuously rather than in single batches, because overall investment and operating costs usually are less. Data obtained in batch reactors, except for very rapid reactions, can be well defined and used to predict performance of larger scale, continuous-flow reactors. Almost all batch reactors are well stirred thus, ideally, compositions are uniform throughout and residence times of all contained reactants are constant. 

The ratio of cycHc to linear oligomers, as well as the chain length of the linear sdoxanes, is controlled by the conditions of hydrolysis, such as the ratio of chlorosilane to water, temperature, contact time, and solvents (60,61). Commercially, hydrolysis of dim ethyl dichi oro sil a n e is performed by either batch or a continuous process (62). In the typical industrial operation, the dimethyl dichi orosilane is mixed with 22% a2eotropic aqueous hydrochloric acid in a continuous reactor. The mixture of hydrolysate and 32% concentrated acid is separated in a decanter. After separation, the anhydrous hydrogen chloride is converted to methyl chloride, which is then reused in the direct process. The hydrolysate is washed for removal of residual acid, neutralized, dried, and filtered (63). The typical yield of cycHc oligomers is between 35 and 50%. The mixture of cycHc oligomers consists mainly of tetramer and pentamer. Only a small amount of cycHc trimer is formed. 

Manufacture. Titanium chloride is manufactured by the chlorination of titanium compounds (1,134—138). The feedstocks usually used are mineral or synthetic mtile, beneficiated ilmenite, and leucoxenes. Because these are all oxygen-containing, it is necessary to add carbon as well as coke from either coal or fuel oil during chlorination to act as a reducing agent. The reaction is normally carried out as a continuous process in a fluid-bed reactor (139). The bed consists of a mixture of the feedstock and coke. These are fluidized by a stream of chlorine iatroduced at the base (see Fluidization). The amount of heat generated in the chlorination process depends on the relative proportions of CO2 or CO that are formed (eqs. 1 and 2), and the mechanism that... 

Titanium disulfide can also be made by pyrolysis of titanium trisulfide at 550°C. A continuous process based on the reaction between titanium tetrachloride vapor and dry, oxygen-free hydrogen sulfide has been developed at pilot scale (173). The preheated reactants ate fed iato a tubular reactor at approximately 500°C. The product particles comprise orthogonally intersecting hexagonal plates or plate segments and have a relatively high surface area (>4 /g), quite different from the flat platelets produced from the reaction between titanium metal and sulfur vapor. The powder, reported to be stable to... 

EPM and EPDM mbbers are produced in continuous processes. Most widely used are solution processes, in which the polymer produced is in the dissolved state in a hydrocarbon solvent (eg, hexane). These processes can be grouped into those in which the reactor is completely filled with the Hquid phase, and those in which the reactor contents consist pardy of gas and pardy of a Hquid phase. In the first case the heat of reaction, ca 2500 kJ (598 kcal)/kg EPDM, is removed by means of cooling systems, either external cooling of the reactor wall or deep-cooling of the reactor feed. In the second case the evaporation heat from unreacted monomers also removes most of the heat of reaction. In other processes using Hquid propylene as a dispersing agent, the polymer is present in the reactor as a suspension. In this case the heat of polymerisation is removed mainly by monomer evaporation. 

The aqueous emulsion polymerization can be conducted by a batch, semibatch, or continuous process (Fig. 5). In a simple batch process, all the ingredients are charged to the reactor, the temperature is raised, and the polymerization is mn to completion. In a semibatch process, all ingredients are charged except the monomers. The monomers are then added continuously to maintain a constant pressure. Once the desired soflds level of the latex is reached (typically 20—40% soflds) the monomer stream is halted, excess monomer is recovered and the latex is isolated. In a continuous process (37), feeding of the ingredients and removal of the polymer latex is continuous through a pressure control or rehef valve. 

Epichlorohydrin Elastomers without AGE. Polymerization on a commercial scale is done as either a solution or slurry process at 40—130°C in an aromatic, ahphatic, or ether solvent. Typical solvents are toluene, benzene, heptane, and diethyl ether. Trialkylaluniinum-water and triaLkylaluminum—water—acetylacetone catalysts are employed. A cationic, coordination mechanism is proposed for chain propagation. The product is isolated by steam coagulation. Polymerization is done as a continuous process in which the solvent, catalyst, and monomer are fed to a back-mixed reactor. Pinal product composition of ECH—EO is determined by careful control of the unreacted, or background, monomer in the reactor. In the manufacture of copolymers, the relative reactivity ratios must be considered. The reactivity ratio of EO to ECH has been estimated to be approximately 7 (35—37). 

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