Paraffins normal separation

Another approach is the simulated moving-bed system, which has large-volume appHcations in normal-paraffin separation andpara- s.yXen.e separation. Since its introduction in 1970, the simulated moving-bed system has largely displaced crystallisation ia xylene separations. The unique feature of the system is that, although the bed is fixed, the feed point shifts to simulate a moving bed (see Adsorption,liquid separation). 

The fifth and final adsorbent characteristic is zeolite type. The adsorbent used in the Molex process is a proprietary and is a particularly effective adsorbent for normal paraffin separation [4, 5] and has achieved purity and recovery targets for the Molex processes. A sampUng of various molecules (and their corresponding dimensions) that Molex can easily separate is listed in Table 8.1. As discussed in Chapter 6, a zeoUtes s pore structure is dependent on its silica aluminum ratio and the proprietary Molex adsorbent possess a uniform repeating three-dimensional porous structure with pores running perpendicular to each other in the x. 

Light Normal Paraffin Separation (Gasoline Range nCs )... 

Normal Paraffin Separations 259 Table 8.3 Research octane number (RON) for C5-C6 hydrocarbons. 

Gas hulk separations normal paraffins, isoparaffins, aromatics zeoHte... 

One version of the UOP IsoSiv process uses PSA to separate normal paraffins from branched and cycHc hydrocarbons in the to range. 

However, ia some cases, the answer is not clear. A variety of factors need to be taken iato consideration before a clear choice emerges. Eor example, UOP s Molex and IsoSiv processes are used to separate normal paraffins from non-normals and aromatics ia feedstocks containing C —C2Q hydrocarbons, and both processes use molecular sieve adsorbents. However, Molex operates ia simulated moving-bed mode ia Hquid phase, and IsoSiv operates ia gas phase, with temperature swiag desorption by a displacement fluid. The foUowiag comparison of UOP s Molex and IsoSiv processes iadicates some of the primary factors that are often used ia decision making ... 

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. 

Separation of Norma/ and Isoparaffins. The recovery of normal paraffins from mixed refinery streams was one of the first commercial appHcations of molecular sieves. Using Type 5A molecular sieve, the / -paraffins can be adsorbed and the branched and cycHc hydrocarbons rejected. During the adsorption step, the effluent contains isoparaffins. During the desorption step, the / -paraffins are recovered. Isothermal operation is typical. 

Chemistry. Chemical separation is achieved by countercurrent Hquid— Hquid extraction and involves the mass transfer of solutes between an aqueous phase and an immiscible organic phase. In the PUREX process, the organic phase is typically a mixture of 30% by volume tri- -butyl phosphate (solvent) and a normal paraffin hydrocarbon (diluent). The latter is typically dodecane or a high grade kerosene (20). A number of other solvent or diluent systems have been investigated, but none has proved to be a substantial improvement (21). 

Norma/andBranc/jedAlip/jatic Hydrocarbons. The urea-adduction method for separating normal and branched aHphatic hydrocarbons can be carried out in sulfolane (38,39). The process obviates the necessity of handling and washing the soHd urea—normal paraffin adduct formed when a solution of urea in sulfolane is contacted with the hydrocarbon mixture. OveraH recovery by this process is typicaHy 85% normal paraffin purity is 98%. 

It is important to note that simulated distillation does not always separate hydrocarbons in the order of their boiling point. For example, high-boihng multiple-ring-type compounds may be eluted earher than normal paraffins (used as the calibration standard) of the same boiling point. Gas chromatography is also used in the ASTM D 2427 test method to determine quantitatively ethane through pentane hydrocarbons. 

J. V. Bmnnock, Separation and distribution of normal paraffins from petroleum heavy distillates by molecular sieve adsorption and gas cliromatogr aphy , Anal. Chem. 38 1648-1652(1966). 

Total Isomerization Also called TIP. An integrated process which combines light paraffin isomerization, using a zeolite catalyst, with the IsoSiv process, which separates the unconverted normal paraffins so that they can be returned to the reactor. Developed by Union Carbide Corporation and now licensed by UOP. The first plant was operated in Japan in 1975 by 1992, more than 25 units had been licensed. 

Examples of rate-selective adsorption are demonstrated using silicalite adsorbent for separation of Ciq-Cm n-paraffins from non- -paraffins [40, 41] and Ciq-Ch mono-methyl-paraffins from non-n-paraffins [42-45]. Silicalite is a ten-ringed zeolite with a pore opening of 5.4A x 5.7 A [22]. In the case of -paraffins/non-n-paraffins separation [40, 41], n-paraffins enter the pores of silicalite freely, but non-n-paraffins such as aromatics, naphthenes and iso-paraffins diffuse into the pores more slowly. However, the diffusion rates of both normal -paraffins and non-n-paraffins increase with temperature. So, one would expect to see minimal separation of n-paraffins from non-n-paraffins at high temperatures but high separation at lower temperature. 

Kulprathipanja, S. (1991) Adsorptive separation process for the purification of heavy normal paraffins with non-normal hydrocarbon pre-pulse stream. U.S. Patent 4,992,618. 

This chapter reviews the adsorptive separations of various classes of non-aromatic hydrocarbons. It covers three different normal paraffin molecular weight separations from feedstocks that range from naphtha to kerosene, the separation of mono-methyl paraffins from kerosene and the separation of mono-olefins both from a mixed C4 stream and from a kerosene stream. In addition, we also review the separation of olefins from a C10-16 stream and review simple carbohydrate separations and various acid separations. 

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