Distillation sieve

Garcia, J. A. 1999. Fundamental Model for the Prediction of Distillation Sieve Tray Efficiency Hydrocarbon and Aqueous Systems. Ph.D. dissertation, Univ. of Texas at Austin. 

Benzene, toluene, and a mixed xylene stream are subsequently recovered by extractive distillation using a solvent. Recovery ofA-xylene from a mixed xylene stream requires a further process step of either crystallization and filtration or adsorption on molecular sieves. o-Xylene can be recovered from the raffinate by fractionation. In A" xylene production it is common to isomerize the / -xylene in order to maximize the production of A xylene and o-xylene. Additional benzene is commonly produced by the hydrodealkylation of toluene to benzene to balance supply and demand. Less common is the hydrodealkylation of xylenes to produce benzene and the disproportionation of toluene to produce xylenes and benzene. 

There are also companies that concentrate on physical operations in connection with fine chemicals manufacturing. Activities include dmg and pesticide formulation, distillation, and milling/sieving/drying. 

Highly pure / -hexane can be produced by adsorption on molecular sieves (qv) (see Adsorption, liquid separation) (43). The pores admit normal paraffins but exclude isoparaffins, cycloparaffins, and aromatics. The normal paraffins are recovered by changing the temperature and/or pressure of the system or by elution with a Hquid that can be easily separated from / -hexane by distillation. Other than ben2ene, commercial hexanes also may contain small concentrations of olefins (qv) and compounds of sulfur, oxygen, and chlorine. These compounds caimot be tolerated in some chemical and solvent appHcations. In such cases, the commercial hexanes must be purified by hydrogenation. 

The extent of purification depends on the use requirements. Generally, either intense aqueous extractive distillation, or post-treatment by fixed-bed absorption (qv) using activated carbon, molecular sieves (qv), and certain metals on carriers, is employed to improve odor and to remove minor impurities. Essence grade is produced by final distillation in nonferrous, eg, copper, equipment (66). 

The separation and analysis of 1-propanol are straightforward. Gas chromatography is the principal method employed. Other iastmmental techniques, eg, nmr, ir, and classical organic quaHtative analysis, are useful. Molecular sieves (qv) have been used to separate 1-propanol from ethanol and methanol. Commercial purification is accompHshed by distillation (qv). 

An enrichment is defined as a separation process that results in the increase in concentration of one or mote species in one product stream and the depletion of the same species in the other product stream. Neither high purity not high recovery of any components is achieved. Gas enrichment can be accompHshed with a wide variety of separation methods including, for example, physical absorption, molecular sieve adsorption, equiHbrium adsorption, cryogenic distillation, condensation, and membrane permeation. 

A sharp separation results in two high purity, high recovery product streams. No restrictions ate placed on the mole fractions of the components to be separated. A separation is considered to be sharp if the ratio of flow rates of a key component in the two products is >10. The separation methods that can potentially obtain a sharp separation in a single step ate physical absorption, molecular sieve adsorption, equiHbrium adsorption, and cryogenic distillation. Chemical absorption is often used to achieve sharp separations, but is generally limited to situations in which the components to be removed ate present in low concentrations. 

A continuous process has been developed for preparing borate esters usiag transesterification (24). Another modification of this method has been reported where use of molecular sieves (qv) to absorb the low boiling alcohol is used rather than distillation (25). 

UOP s Parex Process can be used to purify -xylene by adsorption (38). Toray has a similar process. These processes take advantage of the fact that %xylene is adsorbed more easily than the other Cg aromatics by a suitable molecular sieve. The -xylene is desorbed by either a lighter or heavier hydrocarbon which is subsequently removed by distillation. -Xylene is recovered in about 97% yield (see Adsorption). 

In the physical separation process, a molecular sieve adsorbent is used as in the Union Carbide Olefins Siv process (88—90). Linear butenes are selectively adsorbed, and the isobutylene effluent is distilled to obtain a polymer-grade product. The adsorbent is a synthetic 2eohte, Type 5A in the calcium cation exchanged form (91). UOP also offers an adsorption process, the Sorbutene process (92). The UOP process utilizes ahquid B—B stream, and uses a proprietary rotary valve containing multiple ports, which direct the flow of Hquid to various sections of the adsorber (93,94). The cis- and trans-isomers are alkylated and used in the gasoline blending pool. 

Example 8 Calculation of Rate-Based Distillation The separation of 655 lb mol/h of a bubble-point mixture of 16 mol % toluene, 9.5 mol % methanol, 53.3 mol % styrene, and 21.2 mol % ethylbenzene is to be earned out in a 9.84-ft diameter sieve-tray column having 40 sieve trays with 2-inch high weirs and on 24-inch tray spacing. The column is equipped with a total condenser and a partial reboiler. The feed wiU enter the column on the 21st tray from the top, where the column pressure will be 93 kPa, The bottom-tray pressure is 101 kPa and the top-tray pressure is 86 kPa. The distillate rate wiU be set at 167 lb mol/h in an attempt to obtain a sharp separation between toluene-methanol, which will tend to accumulate in the distillate, and styrene and ethylbenzene. A reflux ratio of 4.8 wiU be used. Plug flow of vapor and complete mixing of liquid wiU be assumed on each tray. K values will be computed from the UNIFAC activity-coefficient method and the Chan-Fair correlation will be used to estimate mass-transfer coefficients. Predict, with a rate-based model, the separation that will be achieved and back-calciilate from the computed tray compositions, the component vapor-phase Miirphree-tray efficiencies. 

Example 9 Loading/Flooding of a Distillation Plate An available sieve plate column of 2.5-m diameter is being considered for an etbylben-zene/styrene separation. An evaluation of loading at the top plate will be made. Key dimensions of the single-crossflow plate are ... 

Direct Scale-Up of Laboratory Distillation Ljficiency Measurements It has been found by Fair, Null, and Bolles [Ind. Eng. Chem. Process Des. Dev., 22, 53 (1983)] that efficiency measurements in 25- and 50-mm (1- and 2-in-) diameter laboratory Oldersbaw columns closely approach tbe point efficiencies [Eq. (14-129)] measured in large sieve-plate columns. A representative comparison of scales of operation is shown in Fig. 14-37. Note that in order to achieve agreement between efficiencies it is necessaiy to ensure that (1) tbe systems being distilled are tbe same, (2) comparison is made at tbe same relative approach to tbe flood point, (3) operation is at total reflux, and (4) a standard Oldersbaw device (a small perforated-plate column with downcomers) is used in tbe laboratoiy experimentation. Fair et al. made careful comparisons for several systems, utibzing as large-scale information tbe published efficiency studies of Fractionation Research, Inc. 

For sieve trays, Chan and Fair [Ind. Eng. Chem. Pioc. Des. Dev., 23, 814 (1983)] used a data bank of larger-scale distillation column efficiencies to deduce the following expression for the product kcCi ... 

The method for estimating point efficiency, outhned here, is not the only approach available for sieve plates, and more mechanistic methods are under development. For example, Prado and Fair [Ind. Eng. Chem. Re.s., 29, 1031 (1990)] have proposed a method whereby bubbling and jetting are taken into account however the method has not been vahdated tor nonaqueous systems. Chen and Chuang [Ind. Eng. Chem. Re.s., 32, 701 (1993)] have proposed a more mechanistic model for predicting point efficiency, but it needs evaluation against a commercial scale distillation data bank. One can expect more development in this area of plate efficiency prediction. 

Product recoveiy from reversed micellar solutions can often be attained by simple back extrac tion, by contacting with an aqueous solution having salt concentration and pH that disfavors protein solu-bihzation, but this is not always a reliable method. Addition of cosolvents such as ethyl acetate or alcohols can lead to a disruption of the micelles and expulsion of the protein species, but this may also lead to protein denaturation. These additives must be removed by distillation, for example, to enable reconstitution of the micellar phase. Temperature increases can similarly lead to product release as a concentrated aqueous solution. Removal of the water from the reversed micelles by molecular sieves or sihca gel has also been found to cause a precipitation of the protein from the organic phase. 

Mallinckrodt AR) which was distilled from KOH and stored over Linde 4A Molecular Sieves. 

The catalyst, 3-benzyl-5-(2-hydroxyethyl )-4-methyl-l, 3-thiazoHum chloride, is supplied by Fluka AG, Buchs, Switzerland, and by Tridom Chemical, Inc., Hauppauge, New York. The thiazolium salt may also be prepared as described below by benzylation of 5-(2-hydroxyethyl)-4-methyl-l,3-thiazole which is commercially available from E. Merck, Darmstadt, West Germany, and Columbia Organic Chemicals Co., Inc., Columbia, SC. The acetonitrile used by the checkers was dried over Linde 3A molecular sieves and distilled under nitrogen, bp 77-78°C. The same yield of thiazolium salt was obtained by the checkers when benzyl chloride and acetonitrile from commercial sources were used without purification. 

To a 3QQ-mL, round-bottomed flask fitted with a water separator, (Note 1) which contains 15 g of Linde 4A molecular sieve l/16-1nch pellets and Is filled with toluene, are added 7.3 g (0.04 mol) of cyclododecanone, 11.4 g (0.16 mol) of pyrrolidine, 100 mL of toluene, and 0.57 g (0.004 mol) of boron trifluoride etherate. The solution is heated under reflux for 20 hr. The water separator is replaced by a distillation head, and about 90 mL of the toluene is removed by distillation at atmospheric pressure. The residue containing l-(N-pyrrolidino)-l-cyclododecene (1) is used in the next step without further purification (Note 2). 

To a solution of 33 g. (O.S mole) of potassium hydroxide (Note 1) in 1.5 1. of distilled water in a 5-1. flask or other appropriate container fitted with a mechanical stirrer is added 80 g. (0.5 mole) of methyl hydrogen adipate (Note 2). With continuous stirring a solution of 85 g. (0.5 mole) of silver nitrate in 1 1. of distilled water is added rapidly (about IS minutes). The precipitated methyl silver adipate is collected on a Buchner funnel, washed with methanol, and dried in an oven at 50-60°. For the next step the dried silver salt is finely powdered and sieved through a 40-mesh screen. The combined yield from two such runs is, 213 g. (80%). 

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