Precipitation process

Precipitation generally refers to a relatively rapid formation of a sparingly soluble solid phase from a liquid solution phase. Precipitation is rather poorly understood when compared with crystallization of more soluble materials. It generally involves the simultaneous and rapid occurrence of nucleation, crystal growth, and other processes, such as Ostwald ripening and agglomeration. All these processes are difficult to separate and independently investigate both mechanistically and experimentally. 

In most practical applications, the properties of the precipitated particles are of key importance and great attention must be paid to particle design or crystal engineering. Many crucial properties of precipitates are physical in nature. The crystal size 

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The precipitation process tends to be complicated when a number of metals are present in solution. If this is the case, then the pH must be adjusted to precipitate out the individual metals, since the pH at which precipitation occurs depends on the metal concerned. 

Selectivity Due to the chemical nature of the precipitation process, precipitants are usually not selective for a single analyte. For example, silver is not a selective precipitant for chloride because it also forms precipitates with bromide and iodide. Consequently, interferents are often a serious problem that must be considered if accurate results are to be obtained. 

Wet Process. The sodium arsenate and stannate slag are treated by a leach and precipitation process to produce calcium arsenate, calcium stannate, and a sodium hydroxide solution for recycle. The sodium antimonate filtercake containing selenium, tellurium, and indium is treated in a special metals refinery to recover indium and tellurium. 

A schematic diagram of the polymer precipitation process is shown in Figure 8. The hot polymer solution is cast onto a water-cooled chill roU, which cools the solution, causing the polymer to precipitate. The precipitated film is passed through an extraction tank containing methanol, ethanol or 2-propanol to remove the solvent. Finally, the membrane is dried, sent to a laser inspection station, trimmed, and roUed up. The process shown in Figure 8... 

In the direct precipitation process, the seeds of iron(III) oxide are added to an iron salt solution, most often iron(II) sulfate, which is subsequendy oxidized by air. The released sulfuric acid is removed by the addition of metallic iron with which it reacts to iron(II) sulfate. The overall reaction shows that ferrous sulfate is not consumed during the process. It only helps to oxidize metallic iron to ferric oxide ... 

Production. Three commercial processes are used for the production of iron yellows the Penniman-Zoph process, the precipitation process, and the Faux process. 

Iron Browns. Iron browns are often prepared by blending red, yellow, and black synthetic iron oxides to the desired shade. The most effective mixing can be achieved by blending iron oxide pastes, rather than dry powders. After mixing, the paste has to be dried at temperatures around 100°C, as higher temperatures might result in the decomposition of the temperature-sensitive iron yellows and blacks. Iron browns can also be prepared directiy by heating hydrated ferric oxides in the presence of phosphoric acid, or alkaU phosphates, under atmospheric or increased pressure. The products of precipitation processes, ie, the yellows, blacks, and browns, can also be calcined to reds and browns. 

Transparent yeUow pigment is composed of needle particles of EeO(OH) having a thickness of 2—5 nm, a width of 10—20 nm, and a length of 50—100 nm. They are prepared by the precipitation process from a very diluted solution of ferrous salt, eg, 6 wt % ferrous sulfate, foUowed by the oxidation of the precipitate with atmospheric oxygen at a temperature of less than 25°C. The precipitate is left to mature for about one day, then filtered, dried, and milled. 

The plutonium extracted by the Purex process usually has been in the form of a concentrated nitrate solution or symp, which must be converted to anhydrous PuF [13842-83-6] or PuF, which are charge materials for metal production. The nitrate solution is sufficientiy pure for the processing to be conducted in gloveboxes without P- or y-shielding (130). The Pu is first precipitated as plutonium(IV) peroxide [12412-68-9], plutonium(Ill) oxalate [56609-10-0], plutonium(IV) oxalate [13278-81-4], or plutonium(Ill) fluoride. These precipitates are converted to anhydrous PuF or PuF. The precipitation process used depends on numerous factors, eg, derived purity of product, safety considerations, ease of recovering wastes, and required process equipment. The peroxide precipitation yields the purest product and generally is the preferred route (131). The peroxide precipitate is converted to PuF by HF—O2 gas or to PuF by HF—H2 gas (31,132). 

Most commercially available RO membranes fall into one of two categories asymmetric membranes containing one polymer, or thin-fHm composite membranes consisting of two or more polymer layers. Asymmetric RO membranes have a thin ( 100 nm) permselective skin layer supported on a more porous sublayer of the same polymer. The dense skin layer determines the fluxes and selectivities of these membranes whereas the porous sublayer serves only as a mechanical support for the skin layer and has Httle effect on the membrane separation properties. Asymmetric membranes are most commonly formed by a phase inversion (polymer precipitation) process (16). In this process, a polymer solution is precipitated into a polymer-rich soHd phase that forms the membrane and a polymer-poor Hquid phase that forms the membrane pores or void spaces. 

Precipitation is affected by pH, solubiUty product of the precipitant, ionic strength and temperature of the aqueous stream, and the presence of metal complexes. For each metal precipitant, there is an optimum pH where its solubiUty is lowest and hence, the highest removals may be achieved. When an aqueous stream contains various metals, the precipitation process caimot be optimized for each metal, sometimes making it difficult to achieve effluent targets for each. SolubiUty products depend on the form of the metal compound and ate lowest for metal sulfides, reflecting the relative insolubiUty of these compounds. For example, the solubiUty product for lead sulfide [1314-87-0] is on the order of compared to 10 for lead carbonate. Metal... 

Fig. 2. Flow sheet for modified jarosite precipitation process.

The method of preparation of a support material has a tremendous effect on its properties (11). For example, zeoHtes, which are highly stmctured aluminosihcates, are known to be extremely sensitive to the conditions employed both during and after crystallization (12). Also, when siUca—titania is precipitated by a coprecipitation method using ammonia, in which localized hydroxide ion gradients are estabUshed by the precipitation process itself, the product is much more acidic than when it is precipitated using urea, which suppHes hydroxide ion slowly and uniformly during precipitation (13). 

In some cases, dye-forming moieties attached to a polymeric backbone, called a polymeric coupler, can replace the monomeric coupler in coupler solvent (51). In other reports, very small particles of coupler solubilized by surfactant micelles can be formed through a catastrophic precipitation process (58). Both approaches can eliminate the need for mechanical manipulation of the coupler phase. 

MetaUic soaps are manufactured by one of three processes a fusion process, a double decomposition or precipitate process, or a direct metal reaction (DMR). The choices of process and solvent depend on the metal, the desired form of the product, the desired purity, raw material avadabihty, and cost. 

Components in which water temperature changes abruptly with distance, such as heat exchangers, tend to accumulate precipitates. Heater surfaces also accumulate precipitates if the dissolved species have inverse temperature solubilities. Systems in which pH excursions are frequent may accumulate deposits due to precipitation processes. Plenum regions, such as heat exchanger headboxes, tend to collect deposits. 

Residuals Produced Resulting metal sludges from the chemical precipitation process may require further treatment prior to disposal. The effluent pH may require an adjustment before it may be discharged. Dissolved inorganics present in the effluent may pose a problem for direct discharge. 

The starting material and shock-activated powder were mixed with 5-wt% MgO and heated for various periods. At the end of each period the phase content of the samples was determined with x-ray diffraction. In this environment it is thought that the phase is formed by a dissolution-precipitation process as shown in Fig. 7.8. As indicated in Fig. 7.9, the shock-activated silicon nitride displays substantially enhanced dissolution rates that are strongly dependent on shock pressure between 22 and 27 GPa. 

This equation describes the change of population in a well-mixed system and is often used to model fully mixed crystallization and precipitation processes. If the system is imperfectly mixed, however, then the more complicated equation 2.88 can be used provided that the external flow field can be calculated e.g. by use of CFD (see later). 

Thus under ideal circumstances the modes of aggregation can be discriminated by such plots. Deviations below the expected slopes are usually attributed to collision inefficiency leading to imperfect aggregation. In a crystallization or precipitation process, of course, deviations may also occur due to growth and nucleation unless properly accounted for. 

In order to describe these different mechanisms, various breakage functions have been proposed (Hill and Ng, 1995, 1996). For precipitation processes, a breakage function of the form given in equation (6.32) with h(v, Xk) being the discretized number fraction of particles broken from size v into size interval x, seems particularly suitable as both attrition - with a high probability - and particle splitting - with a low probability - are accounted for. 

Using the SFM, the influence of micromixing and mesomixing on the precipitation process and properties of the precipitate can be investigated. Mass and population balances can be applied to the individual compartments and to the overall reactor accounting for different levels of supersaturation in different zones of the reactor. 

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