Precipitation reactors

Example of Application of the Growth Ramp. The experimental verification of the growth ramp equation, Eq. (6.56), was carried out by Karpinski (1996), for octahedral and cubic AgBr submicron crystals in a 6.0-1 batch reactor-precipitator. In the preliminary experiments, the number and size of the effective (stable) nuclei were determined. To this end, trial precipitations were performed with samples for sizing taken just prior to the growth stage and at the end of precipitation. The size was measured by a disc centrifuge-sizer, and the number of crystals was determined from the material balance. 

The advantages of the knotted reactor precipitate collector may be summarized as follows ... 

Fig.7 Schematic diagram of a FI filterless on-line precipitation system with precipitate dissolution using a knoned reactor (KR) as precipitate collector, a. sample loading (precipitate collection) sequence b, precipitate dissolution sequence. Pi. P2. peristaltic pumps V. 4 5 channel injector valve PR. precipitant S. sample R. buffer reagent (optional) DS, dissolution solvent KR, knoned reactor precipitate collector and W, waste [21].

Solid products precipitated from a liquid or gaseous reaction mixture often have the form of fine particles, that have to be separated afterwards. There are many examples of precipitations from solutions, both in organic and inorganic chemistry. Such precipitations are often carried out in stirred reactors. Precipitations from gaseous mixtures are less conunon they may be carried out in tubular reactors or in fluidized bed reactors. 

A better alternative is often to divide the variables into conceptually meaningful blocks, and then apply hierarchical multi-block PLS (or PC) models. In QSAR the blocks may correspond to different regions of the modeled molecules and different types of variable (size descriptors, polarity descriptors, etc.), and in multivariate calibration the blocks may correspond to different spectral regions. In process modeling, the process usually has a number of different steps (e.g., raw material, reactor, precipitation step), and variables measured on these different steps constitute natural blocks. These may be divided further according to the type of variables (e.g., temperatures, flows, pressures, concentrations). 

In production, anhydrous formaldehyde is continuously fed to a reactor containing well-agitated inert solvent, especially a hydrocarbon, in which monomer is sparingly soluble. Initiator, especially amine, and chain-transfer agent are also fed to the reactor (5,16,17). The reaction is quite exothermic and polymerisation temperature is maintained below 75°C (typically near 40°C) by evaporation of the solvent. Polymer is not soluble in the solvent and precipitates early in the reaction. 

The enthalpy of the copolymerization of trioxane is such that bulk polymerization is feasible. For production, molten trioxane, initiator, and comonomer are fed to the reactor a chain-transfer agent is in eluded if desired. Polymerization proceeds in bulk with precipitation of polymer and the reactor must supply enough shearing to continually break up the polymer bed, reduce particle size, and provide good heat transfer. The mixing requirements for the bulk polymerization of trioxane have been reviewed (22). Raw copolymer is obtained as fine emmb or flake containing imbibed formaldehyde and trioxane which are substantially removed in subsequent treatments which may be combined with removal of unstable end groups. 

Catalyst recovery is a major operational problem because rhodium is a cosdy noble metal and every trace must be recovered for an economic process. Several methods have been patented (44—46). The catalyst is often reactivated by heating in the presence of an alcohol. In another technique, water is added to the homogeneous catalyst solution so that the rhodium compounds precipitate. Another way to separate rhodium involves a two-phase Hquid such as the immiscible mixture of octane or cyclohexane and aliphatic alcohols having 4—8 carbon atoms. In a typical instance, the carbonylation reactor is operated so the desired products and other low boiling materials are flash-distilled. The reacting mixture itself may be boiled, or a sidestream can be distilled, returning the heavy ends to the reactor. In either case, the heavier materials tend to accumulate. A part of these materials is separated, then concentrated to leave only the heaviest residues, and treated with the immiscible Hquid pair. The rhodium precipitates and is taken up in anhydride for recycling. 

The wastes from uranium and plutonium processing of the reactor fuel usually contain the neptunium. Precipitation, solvent extraction, ion exchange, and volatihty procedures (see Diffusion separation methods) can be used to isolate and purify the neptunium. 

Kilogram quantities of americium as Am can be obtained by the processing of reactor-produced plutonium. Much of this material contains an appreciable proportion of Pu, which is the parent of Am. Separation of the americium is effected by precipitation, ion exchange, or solvent extraction. 

The bulk polycondensation of (10) is normally carried out in evacuated, sealed vessels such as glass ampules or stainless steel Parr reactors, at temperatures between 160 and 220°C for 2—12 d (67). Two monomers with different substituents on each can be cocondensed to yield random copolymers. The by-product sdyl ether is readily removed under reduced pressure, and the polymer purified by precipitation from appropriate solvents. Catalysis of the polycondensation of (10) by phenoxide ion in particular, as well as by other species, has been reported to bring about complete polymerisation in 24—48 h at 150°C (68). Catalysis of the polycondensation of phosphoranimines that are similar to (10), but which yield P—O-substituted polymers (1), has also been described and appears promising for the synthesis of (1) with controlled stmctures (69,70). 

Up to 0.4 g/L of the iodine stays in solution and the rest precipitates as crystallized iodine, which is removed by flotation (qv). This operation does not require a flotation agent, owing to the hydrophobic character of the crystallized element. From the flotation cell a heavy pulp, which is water-washed and submitted to a second flotation step, is obtained. The washed pulp is introduced into a heat exchanger where it is heated under pressure up to 120°C to melt the iodine that flows into a first reactor for decantation. From there the melt flows into a second reactor for sulfuric acid drying. The refined iodine is either flaked or prilled, and packed in 50- and 25-kg plastic-lined fiber dmms. 

The softened seawater is fed with dry or slaked lime (dolime) to a reactor. After precipitation in the reactor, a flocculating agent is added and the slurry is pumped to a thickener where the precipitate settles. The spent seawater overflows the thickener and is returned to the sea. A portion of the thickener underflow is recirculated to the reactor to seed crystal growth and improve settling and filtering characteristics of the precipitate. The remainder of the thickener underflow is pumped to a countercurrent washing system. In this system the slurry is washed with freshwater to remove the soluble salts. The washed slurry is vacuum-filtered to produce a filter cake that contains about 50% Mg(OH)2. Typical dimensions for equipment used in the seawater process may be found in the Hterature (75). 

Plutonium. The plutonium nitrate product must be converted to MO fuel if it is to be recycled to lightwater reactors. Whether from a plutonium nitrate solution or a mixed U/Pu nitrate solution, the plutonium is typically precipitated as the oxalate and subsequendy calcined to the oxide for return to the fuel cycle (33). 

Ammonia, hydrochloric acid, and sodium perchlorate are mixed and the reaction mixture crystallised in a vacuum-cooled crystalliser. Ammonium perchlorate crystals are centrifuged, reslurried, recentrifuged, and then dried and blended for shipment. Mother Hquor is evaporated to precipitate sodium chloride and the depleted mother Hquor is recycled to the reactor. The AP product made by this method is 99% pure and meets the specifications for propeUant-grade ammonium perchlorate. The impurities are ammonium chloride, sodium perchlorate, ammonium chlorate, and water insolubles. 

Selenium and precious metals can be removed selectively from the chlorination Hquor by reduction with sulfur dioxide. However, conditions of acidity, temperature, and a rate of reduction must be carefliUy controlled to avoid the formation of selenium monochloride, which reacts with elemental selenium already generated to form a tar-like substance. This tar gradually hardens to form an intractable mass which must be chipped from the reactor. Under proper conditions of precipitation, a selenium/precious metals product substantially free of other impurities can be obtained. Selenium can be recovered in a pure state by vacuum distillation, leaving behind a precious metals residue. 

Fig. 13. Schematic of precipitated sihca production (54), where H =, eg, reactor, washer, filter, and dryer Q = pump or transfer device, eg, bucket elevator...

After the SO converter has stabilized, the 6—7% SO gas stream can be further diluted with dry air, I, to provide the SO reaction gas at a prescribed concentration, ca 4 vol % for LAB sulfonation and ca 2.5% for alcohol ethoxylate sulfation. The molten sulfur is accurately measured and controlled by mass flow meters. The organic feedstock is also accurately controlled by mass flow meters and a variable speed-driven gear pump. The high velocity SO reaction gas and organic feedstock are introduced into the top of the sulfonation reactor,, in cocurrent downward flow where the reaction product and gas are separated in a cyclone separator, K, then pumped to a cooler, L, and circulated back into a quench cooling reservoir at the base of the reactor, unique to Chemithon concentric reactor systems. The gas stream from the cyclone separator, M, is sent to an electrostatic precipitator (ESP), N, which removes entrained acidic organics, and then sent to the packed tower, H, where SO2 and any SO traces are adsorbed in a dilute NaOH solution and finally vented, O. Even a 99% conversion of SO2 to SO contributes ca 500 ppm SO2 to the effluent gas. 

Caustic soda is removed from the carbonate—bicarbonate solution by treating with a slight excess of hard-burned quicklime (or slaked lime) at 85—90°C in a stirred reactor. The regenerated caustic soda is separated from the calcium carbonate precipitate (lime mud) by centrifuging or rotary vacuum filtration. The lime mud retains 30—35% Hquid and, to avoid loss of caustic soda, must be weU-washed on the filter or centrifuge. Finally, the recovered caustic solution is adjusted to the 10% level for recycle by the addition of 40% makeup caustic soda. 

Polymerization Kinetics of Mass and Suspension PVC. The polymerization kinetics of mass and suspension PVC are considered together because a droplet of monomer in suspension polymerization can be considered to be a mass polymerization in a very tiny reactor. During polymerization, the polymer precipitates from the monomer when the chain size reaches 10—20 monomer units. The precipitated polymer remains swollen with monomer, but has a reduced radical termination rate. This leads to a higher concentration of radicals in the polymer gel and an increased polymerization rate at higher polymerization conversion. 

Qua.driva.Ient, Zirconium tetrafluoride is prepared by fluorination of zirconium metal, but this is hampered by the low volatility of the tetrafluoride which coats the surface of the metal. An effective method is the halogen exchange between flowing hydrogen fluoride gas and zirconium tetrachloride at 300°C. Large volumes are produced by the addition of concentrated hydrofluoric acid to a concentrated nitric acid solution of zirconium zirconium tetrafluoride monohydrate [14956-11-3] precipitates (69). The recovered crystals ate dried and treated with hydrogen fluoride gas at 450°C in a fluid-bed reactor. The thermal dissociation of fluorozirconates also yields zirconium tetrafluoride. 

Precipitated Calcium Carbonate. Precipitated calcium carbonate can be produced by several methods but only the carbonation process is commercially used in the United States. Limestone is calcined in a kiln to obtain carbon dioxide and quicklime. The quicklime is mixed with water to produce a milk-of-lime. Dry hydrated lime can also be used as a feedstock. Carbon dioxide gas is bubbled through the milk-of-lime in a reactor known as a carbonator. Gassing continues until the calcium hydroxide has been converted to the carbonate. The end point can be monitored chemically or by pH measurements. Reaction conditions determine the type of crystal, the size of particles, and the size distribution produced. 

The Tj-carbides are not specifically synthesized, but are of technical importance, occurring in alloy steels, stelUtes, or as embrittling phases in cemented carbides. Other complex carbides in the form of precipitates may form in multicomponent alloys or in high temperature reactor fuels by reaction between the fission products and the moderator graphite, ie, pyrographite-coated fuel kernels. 

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). 

Fig. 13. Flowsheet of medium pressure synthesis, fixed-bed reactor (Lurgi-Ruhrchemie-Sasol) having process conditions for SASOL I of an alkaline, precipitated-iron catalyst, reduction degree 20—25% having a catalyst charge of 32—36 t, at 220—255°C and 2.48 MPa (360 psig) at a fresh feed rate of...

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