Solution process Solvent

Solute Process" Solvent" (extractant/diluent) Contactor type" Literature... 

Semibatch solution polymerization is a well-established method for producing acrylic resins. In the semibatch solution process, solvent is commonly charged to the reactor and heated to the desired reaction temperature, typically 100-140 °C. Monomer, initiator, and other ingredients are slowly fed to the reactor over a period of 4-6 h to achieve a desired solids content (typically up to 70% by weight solids). During polymerization, the solvent may be refluxed to help remove the heat of polymerization [40]. At the end of the polymerization, a hold time and post charge of initiator solution are common to techniques designed to reduce... 

Liquids by liquids. The apparatus represented by Fig. 11, 58, 3 is employed for the extraction of aqueous solutions by solvents lighter than water, such as ether or benzene. The solvent distilled from the flask (attached to the lower end) and condensed by the reflux condenser (fltted to the upper end) passes through the funnel down a narrow tube, partially open at the lower end, into the aqueous solution, then rises to the surface and returns to the flask, having during its passage extracted some portion of the dissolved material from it. To improve the efficiency of the process. 

Other Organic Processes. Solvent extraction has found appHcation in the coal-tar industry for many years, as for example in the recovery of phenols from coal-tar distillates by washing with caustic soda solution. Solvent extraction of fatty and resimic acid from tall oil has been reported (250). Dissociation extraction is used to separate y -cresol fromT -cresol (251) and 2,4-x5lenol from 2,5-x5lenol (252). Solvent extraction can play a role in the direct manufacture of chemicals from coal (253) (see Eeedstocks, coal chemicals). 

If the solute is uniformly distributed through the soHd phase the material near the surface dissolves first to leave a porous stmcture in the soHd residue. In order to reach further solute the solvent has to penetrate this outer porous region the process becomes progressively more difficult and the rate of extraction decreases. If the solute forms a large proportion of the volume of the original particle, its removal can destroy the stmcture of the particle which may cmmble away, and further solute maybe easily accessed by solvent. In such cases the extraction rate does not fall as rapidly. 

In general, the foUowing steps can occur in an overall Hquid—soHd extraction process solvent transfer from the bulk of the solution to the surface of the soHd penetration or diffusion of the solvent into the pores of the soHd dissolution of the solvent into the solute solute diffusion to the surface of the particle and solute transfer to the bulk of the solution. The various fundamental mechanisms and processes involved in these steps make it impracticable or impossible to describe leaching by any rigorous theory. 

The sohd can be contacted with the solvent in a number of different ways but traditionally that part of the solvent retained by the sohd is referred to as the underflow or holdup, whereas the sohd-free solute-laden solvent separated from the sohd after extraction is called the overflow. The holdup of bound hquor plays a vital role in the estimation of separation performance. In practice both static and dynamic holdup are measured in a process study, other parameters of importance being the relationship of holdup to drainage time and percolation rate. The results of such studies permit conclusions to be drawn about the feasibihty of extraction by percolation, the holdup of different bed heights of material prepared for extraction, and the relationship between solute content of the hquor and holdup. If the percolation rate is very low (in the case of oilseeds a minimum percolation rate of 3 x 10 m/s is normally required), extraction by immersion may be more effective. Percolation rate measurements and the methods of utilizing the data have been reported (8,9) these indicate that the effect of solute concentration on holdup plays an important part in determining the solute concentration in the hquor leaving the extractor. 

Most cellulose acetate is manufactured by a solution process, ie, the cellulose acetate dissolves as it is produced. The cellulose is acetylated with acetic anhydride acetic acid is the solvent and sulfuric acid the catalyst. The latter can be present at 10—15 wt % based on cellulose (high catalyst process) or at ca 7 wt % (low catalyst process). In the second most common process, the solvent process, methylene chloride replaces the acetic acid as solvent, and perchloric acid is frequentiy the catalyst. There is also a seldom used heterogeneous process that employs an organic solvent as the medium, and the cellulose acetate produced never dissolves. More detailed information on these processes can be found in Reference 28. 

The solution process consists of four steps preparation of cellulose for acetylation, acetylation, hydrolysis, and recovery of cellulose acetate polymer and solvents. A schematic of the total acetate process is shown in Figure 9. 

Solution Polymerization. Two solution polymerization technologies ate practiced. Processes of the first type utilize heavy solvents those of the second use molten PE as the polymerization medium (57). Polyethylene becomes soluble ia saturated C —hydrocarbons above 120—130°C. Because the viscosity of HDPE solutions rapidly iacrease with molecular weight, solution polymerization is employed primarily for the production of low mol wt resias. Solution process plants were first constmcted for the low pressure manufacture of PE resias ia the late 1950s they were later exteasively modified to make their operatioa economically competitive. 

Solution Polymerization. Two types of solution polymerization technologies are used for LLDPE synthesis. One process utilizes heavy solvents the other is carried out in mixtures of supercritical ethylene and molten PE as a polymerization medium. Original solution processes were introduced for low pressure manufacture of PE resins in the late 1950s subsequent improvements of these processes gradually made them economically competitive with later, more advanced technologies. 

In the early 1990s, solution processes acquired new importance because of their shorter residence times and abiUty to accommodate metallocene catalysts. Many heterogeneous multicenter Ziegler catalysts produce superior LLDPE resins with a better branching uniformity if the catalyst residence time in a reactor is short. Solution processes usually operate at residence times of around 5—10 min or less and are ideal for this catalyst behavior. Solution processes, both in heavy solvents and in the polymer melt, are inherently suitable to accommodate soluble metallocene catalysts (52). For this reason, these processes were the first to employ metallocene catalysts for LLDPE and VLDPE manufacture. 

Eastman Chemical has utilized a unique, high temperature solution process for propylene polymerization. Polymerization temperatures are maintained above 150°C to prevent precipitation of the isotactic polypropylene product in the hydrocarbon solvent. At these temperatures, the high rate of polymerization decreases rapidly, requiring low residence times (127). Stereoregularity is also adversely affected by high temperatures. Consequentiy, the... 

The principle of solvent extraction in refining is as follows when a dilute aqueous metal solution is contacted with a suitable extractant, often an amine or oxime, dissolved in a water-immiscible organic solvent, the metal ion is complexed by the extractant and becomes preferentially soluble in the organic phase. The organic and aqueous phases are then separated. By adding another aqueous component, the metal ions can be stripped back into the aqueous phase and hence recovered. Upon the identification of suitable extractants, and using a multistage process, solvent extraction can be used to extract individual metals from a mixture. 

Process Solvent Solution circulation Acid gas content in treated gas, ppm ... 

A reverse osmosis membrane acts as the semipermeable barrier to flow ia the RO process, aHowiag selective passage of a particular species, usually water, while partially or completely retaining other species, ie, solutes such as salts. Chemical potential gradients across the membrane provide the driving forces for solute and solvent transport across the membrane. The solute chemical potential gradient, —is usually expressed ia terms of concentration the water (solvent) chemical potential gradient, —Afi, is usually expressed ia terms of pressure difference across the membrane. 

Ultrafiltration separations range from ca 1 to 100 nm. Above ca 50 nm, the process is often known as microfiltration. Transport through ultrafiltration and microfiltration membranes is described by pore-flow models. Below ca 2 nm, interactions between the membrane material and the solute and solvent become significant. That process, called reverse osmosis or hyperfiltration, is best described by solution—diffusion mechanisms. 

Solvent Extraction. Solvent extraction has widespread appHcation for uranium recovery from ores. In contrast to ion exchange, which is a batch process, solvent extraction can be operated in a continuous countercurrent-fiow manner. However, solvent extraction has a large disadvantage, owing to incomplete phase separation because of solubihty and the formation of emulsions. These effects, as well as solvent losses, result in financial losses and a potential pollution problem inherent in the disposal of spent leach solutions. For leach solutions with a concentration greater than 1 g U/L, solvent extraction is preferred. For low grade solutions with <1 g U/L and carbonate leach solutions, ion exchange is preferred (23). Solvent extraction has not proven economically useful for carbonate solutions. 

Solution Process. With the exception of fibrous triacetate, practically all cellulose acetate is manufactured by a solution process using sulfuric acid catalyst with acetic anhydride in an acetic acid solvent. An excellent description of this process is given (85). In the process (Fig. 8), cellulose (ca 400 kg) is treated with ca 1200 kg acetic anhydride in 1600 kg acetic acid solvent and 28—40 kg sulfuric acid (7—10% based on cellulose) as catalyst. During the exothermic reaction, the temperature is controlled at 40—45°C to minimize cellulose degradation. After the reaction solution becomes clear and fiber-free and the desired viscosity has been achieved, sufficient aqueous acetic acid (60—70% acid) is added to destroy the excess anhydride and provide 10—15% free water for hydrolysis. At this point, the sulfuric acid catalyst may be partially neutralized with calcium, magnesium, or sodium salts for better control of product molecular weight. 

Reverse Osmosis and Ultrafiltration. Reverse osmosis (qv) (or hyperfiltration) and ultrafilttation (qv) ate pressure driven membrane processes that have become well estabUshed ia pollution control (89—94). There is no sharp distinction between the two both processes remove solutes from solution. Whereas ultrafiltration usually implies the separation of macromolecules from relatively low molecular-weight solvent, reverse osmosis normally refers to the separation of the solute and solvent molecules within the same order of magnitude in molecular weight (95) (see also Membrane technology). 

Several patents describe solvent-free bulk-phase halogenation (67—69). Dry soHd butyl mbber is fed into a specially designed extmder reactor and contacted with chlorine or bromine vapor. The by-product HCl or HBr ate vented directly without a separate neutralization step. Halogenated butyl mbbers produced are essentially comparable in composition and properties to commercial products made by the solution process. 

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. 

Solution processes are used mainly for coating, film casting and fibre spinning, i.e. in processes where the distance the solvent has to diffuse out of the solution once coated, cast or spun is short. Regulation of this diffusion process is important if products of even quality are to be obtained. 

The photochemistry of carbonyl compounds has been extensively studied, both in solution and in the gas phase. It is not surprising that there are major differences between the photochemical reactions in the two phases. In the gas phase, the energy transferred by excitation cannot be lost rapidly by collision, whereas in the liquid phase the excess energy is rapidly transferred to the solvent or to other components of the solution. Solution photochemistry will be emphasized here, since both mechanistic study and preparative applications of organic reactions usually involve solution processes. 

A useful property of liquids is their ability to dissolve gases, other liquids and solids. The solutions produced may be end-products, e.g. carbonated drinks, paints, disinfectants or the process itself may serve a useful function, e.g. pickling of metals, removal of pollutant gas from air by absorption (Chapter 17), leaching of a constituent from bulk solid. Clearly a solution s properties can differ significantly from the individual constituents. Solvents are covalent compounds in which molecules are much closer together than in a gas and the intermolecular forces are therefore relatively strong. When the molecules of a covalent solute are physically and chemically similar to those of a liquid solvent the intermolecular forces of each are the same and the solute and solvent will usually mix readily with each other. The quantity of solute in solvent is often expressed as a concentration, e.g. in grams/litre. 

Through these processes dissolved substances and/or finely dispersed particles can be separated from liquids. All five technologies rely on membrane transport, the passage of solutes or solvents through thin, porous polymeric membranes. 

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