Molex process

Molex process separation [ADSORPTION, LIQUID SEPABA.TION] (Voll)... 

In contrast to trace impurity removal, the use of adsorption for bulk separation in the liquid phase on a commercial scale is a relatively recent development. The first commercial operation occurred in 1964 with the advent of the UOP Molex process for recovery of high purity / -paraffins (6—8). Since that time, bulk adsorptive separation of liquids has been used to solve a broad range of problems, including individual isomer separations and class separations. The commercial availability of synthetic molecular sieves and ion-exchange resins and the development of novel process concepts have been the two significant factors in the success of these processes. This article is devoted mainly to the theory and operation of these Hquid-phase bulk adsorptive separation processes. 

Fig. 13. UOP Penex-Molex process. AC = adsorbent chamber, EC = extract column, RC = raffinate column.

Linear paraffins in the C q to range are used for the production of alcohols and plasticizers and biodegradable detergents of the linear alkylbenzene sulfonate and nonionic types (see Alcohols Plasticizers Surfactants). Here the UOP Molex process is used to extract / -paraffins from a hydrotreated kerosine (6—8). 

The fermentation of / -paraffins in the C q to range for protein production has provided a new oudet for these hydrocarbons (see Foods, nonconventional). Because it operates in Hquid phase, the UOP Molex process can readily accomplish the separation of / -paraffins from such a wide boiling feedstock. 

In terms of the production of olefins suitable for use as alkylation reagents in the synthesis of LAB, the Olex part of the process is of low priority. The olefins produced here are used mainly in the manufacture of oxoalcohols. The separation of the olefins from the paraffins proceeds by the same technology as that developed for the Molex process with the difference being that the sepa-... 

In this particular case, the adsorption process can be used to overcome the distillation limitation. This is demonstrated in Figure 6.2, which represents the relative adsorption of C5 and C(, Hnear, branched and cycHc paraffins from the liquid phase of the 5A adsorbent used in the HOP GasoHne Molex process, licensed by HOP. In this process, only Hnear paraffins can enter the pores of 5A zeolite, while branched and cyclic paraffins are completely excluded due to their large kinetic diameters. Also, the selectivity for Hnear paraffins with respect to other types of paraffins is infinite. Consequently, the separation of Hnear paraffins from branched and cyclic paraffins becomes possible. 

Figure 6.2 illustrates the separation of n-Csis and non-n-Cs/is in CaA molecular sieves or 5A. The separation mechanism is obvious when the kinetic diameter of the molecules and molecular sieve pore size opening are compared. n-Csjc have kinetic diameters of less than 4.4 A which can diffuse freely into the 4.7 A pores of the CaA molecular sieve, while non-n-Cs/ have kinetic diameters of 6.2A. A commercial example of shape-selective adsorption is the UOP Molex process, which uses CaA molecular sieves to separate Cio-C n-paraffins from non- -parafHns (aromatics, branched, naphthenes). 

Each Molex process employs a unique set of process operating conditions, process configuration and desorbent. The specific process details for each of the three n-paraffin separation process are revealed in this chapter, but before we review these details, we first discuss the important adsorbent and desorbent performance characteristics that are common to all. 

Selectivity is a relative term and is defined in the Molex process as the adsorbent s preference for desired component (in this case, normal paraffins) over the undesired feed components (cyclic paraffins, iso-paraffins, aromatics) while employing a particular desorbent. One can easily determine an adsorbent and desorbent combination selectivity using a pulse test screening apparatus. This apparatus consists of a known volume of adsorbent placed in a fixed bed. A stream of desorbent is then passed over the bed to fill the pore and interstitial volume of the bed. A known quantity of feed is introduced to the feed at the top of the adsorbent bed and passed across the column as a pulse of feed. This pulse of feed is then pushed through the adsorbent bed using a known desorbent flow rate. Effluent from the column is monitored for the various feed components and the concentrations of each component noted (with respect to time) as they elude from the... 

In the case of the Molex process, the pulse test separation between the desired normal paraffins and the non-normal feed components produces discrete and separate peaks. This high degree of separation means a Molex unit can achieve high degrees of purity and recovery but the ultimate purity and recovery are dictated by non-ideal conditions such as back mixing or flow mal-distributions. 

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. 

Since the Sorbex process is a liquid-phase fixed-bed process, the selection of particle size is an important consideration for pressure drop and process hydraulics. The exact particle size is optimized for each particular Molex process to balance the liquid phase diffusion rates and adsorbent bed frictional pressure drop. The Sorbex process consists of a finite number of interconnected adsorbent beds. These beds are allocated between the following four Sorbex zones zone 1 is identified as the adsorption zone, zone 2 is identified as the purification zone, zone 3 is identified as the desorption and zone 4 is identified as the buffer zone. The total number of beds and their allocation between the different Sorbex zones is dependent on the desired performance of the particular Molex process. Molex process performance is defined by two parameters extract normal paraffin purity and degree of normal paraffin recovery from the corresponding feedstock. Details about the zone and the bed allocations for each Molex process are covered in subsequent discussions about each process. 

Like the criteria for adsorbent selection, there are criteria for desorbent selection. For the Molex process this is covered by the following five main performance... 

Figure 8.2 depicts the four main zones and their immediate proximity to each other in the Molex process. As indicated earlier, the Sorbex process operates on a liquid-solid countercurrent contacting principle. Zone 1 is referred to as the... 

Common to aU Molex processes are the following six Sorbex zone parameters A, F , A/F , D , D /A and cycle time. 

The second of the six Sorbex zone parameters is F , which represents the volumetric rate of feed normals introduced to the Molex process. 

The gasoline Molex process is the first of three processes since it separates the lowest molecular weight feed of the three Molex normal paraffin separahon processes. Gasoline Molex was developed to optimize a Refiner s octane pool by extracting low octane value normal paraffins (specifically C5, 5) from naphtha. In a typical refinery flow scheme, a gasoline Molex unit is integrated with a catalyhc isomeriza-hon unit (Penex unit) which converts the Molex unit s extracted normal paraffins into desired iso-paraffins. These iso-paraffins are desirable because they possess higher octane value than their linear counterpart. 

Unlike the gasoline Molex process that employs a iso-butane and n-butane desorbent mixture, the MaxEne process employs a heavy desorbent system. A heavy desorbent system means that the bottom product from both the Sorbex extract and raffinate frachonation columns is desorbent while the feed components are recovered as overhead products. In the MaxEne process case, heavy normal paraffin such as n-dodecane is employed as the desorbent though desorbents as light as n-decane and as heavy as n-tetradecane are possible candidates too. 

Since the detergent Molex process is both a high normal paraffin purity and recovery process, it is designed with the full allotment of Sorbex beds in addition to the four basic Sorbex zones. The detergent Molex process utilizes a split desorbent. This means it consists of a mixture of n-pentane and iso-octane. The zone flush primarily consists of isooctane and its purpose is to keep the desorbent (n-... 

The MMP Sorbex process has many similarities but also some differences when compared to the detergent Molex process. As with all of Sorbex processes, the MMP Sorbex process operates in the Uquid phase, employing suitable conditions (pressure, temperature) to overcome any diffusion constraints to achieve target performance. Table 8.4 highlights and contrasts the different characteristics of the detergent Molex and MMP Sorbex processes. The process was successfully demonstrated in a continuous countercurrent moving bed separation pilot plant using commercial n-paraffin-depleted kerosene (Molex raffinate) feedstock. A typical gas... 

Sohn, S.W. (2003) UOP molex process for production of normal paraffins, in... 

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