Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 10.3

UOP SORBEX FAMILY OF TECHNOLOGIES

James A. Johnson
UOP LLC Des Plaines, Illinois

INTRODUCTION
The Sorbex* name is applied to a technique, developed by UOP,* that is used to separate a component or group of components from a mixture by selective adsorption on a solid adsorbent. The Sorbex technology is a continuous process in which feed and products enter and leave the adsorbent bed at substantially constant composition. This technology simulates the countercurrent flow of a liquid feed over a solid bed of adsorbent without physically moving the solid. The principles of Sorbex technology are the same regardless of the type of separation being conducted. The following are examples of commercially proven UOP technologies based on the Sorbex principle; each makes use of a specific adsorbent-desorbent combination uniquely tailored to the specific separation:

Parex*: separation of para-xylene from mixed C8 aromatic isomers MX Sorbex*: meta-xylene from mixed C8 aromatic isomers Molex*: linear paraffins from branched and cyclic hydrocarbons Olex*: olefins from paraffins Cresex*: para-cresol or meta-cresol from other cresol isomers Cymex*: para-cymene or meta-cymene from other cymene isomers Sarex*: fructose from mixed sugars

In addition to these applications, numerous other commercially interesting separations have been identified and demonstrated using the Sorbex process. These applications include monomethyl paraffins, 2,6-dimethyl naphthalene, ethylbenzene, 1-butene, ethyl toluenes, toluidines, terpenes, chloro and nitro aromatics, alpha and beta naphthols, alkyl naphthalenes, alpha olefins, and tall oil. Some of these separations have been commercialized under tolling agreements at a large-scale Sorbex plant that UOP has operated in Shreveport, Louisiana.
*Trademark and/or service mark of UOP.

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UOP SORBEX FAMILY OF TECHNOLOGIES 10.30

SEPARATION PROCESSES

The general principles of Sorbex technology are described in this chapter. Specific details on some of the Sorbex applications may be found in Chaps. 2.6 and 10.7.

PRINCIPLES OF ADSORPTIVE SEPARATION

Adsorbents can be visualized as porous solids. When the adsorbent is immersed in a liquid mixture, the pores fill with liquid, but the equilibrium distribution of components inside the pore is different from the distribution in the surrounding bulk liquid. The component distributions inside and outside the pores can be related to one another by enrichment factors analogous to relative volatilities in distillation. The adsorbent is said to be selective for any components that are more concentrated inside the pores than in the surrounding bulk liquid. Adsorption has long been used for the removal of contaminants present at low concentrations in process streams. In some instances, the objective is removal of specific compounds. In other cases, the objective is improvement of general properties, such as color, taste, odor, or storage stability. Common adsorbents are generally classified as polar or nonpolar. Polar, or hydrophilic, adsorbents include silica gel, activated alumina, molecular sieves, and various clays. Nonpolar adsorbents include activated carbons and other types of coal-derived carbons. Polar adsorbents are used when the components to be removed are more polar than the bulk process liquid; nonpolar adsorbents are used when the target components are less polar. Particularly useful are those adsorbents based on synthetic crystalline zeolites, which are generically referred to as molecular sieves. A wide variety of selectivities can be obtained in molecular sieves by varying the silica/alumina ratio, crystalline structure, and nature of the replaceable cations in the crystal lattice. In one commercial separation, linear paraffins are separated from branched-chain and cyclic hydrocarbons by adsorption on 5A molecular sieves. The diameter of the pores is such that only the linear molecules may enter, and branched or cyclic molecules are completely excluded. In this case, the selectivity for linear hydrocarbons is infinite, and the adsorbent acts as a true molecular sieve. Adsorbents that completely exclude unwanted components are rare. In most applications, the pores are large enough to admit molecules of all the components present, and selectivity is the result of electronic interactions between the surface of the adsorbent pores and the individual components. Adsorption is more efficient than conventional techniques such as liquid-liquid extraction or extractive distillation for many commercially important separations. Considerable development work has identified many adsorbents that are much more selective for specific components than any known solvents. In addition, adsorptive separation exhibits much higher mass-transfer efficiency than conventional extraction or extractive distillation. For example, laboratory chromatographs commonly achieve separation efficiencies equivalent to many thousands of theoretical equilibrium stages in columns of modest length. Such high mass-transfer efficiency stems from the use of small particles of adsorbent with high interfacial area and the absence of significant axial mixing. In contrast, the trays of conventional liquid-liquid extractors and distillation columns are designed to obtain almost complete axial mixing in each physical stage. Thus, the number of theoretical equilibrium stages is essentially limited to the number of physical stages installed. In theory, this limitation can be partly overcome by the use of packed columns. However, if the packing is small enough to provide interfacial area comparable to that of an adsorbent, maintaining uniform countercurrent flow of the vapor and liquid phases becomes difficult. This flow limitation is less troublesome in an adsorptive system because only one fluid phase is involved.

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10.31

THE SORBEX CONCEPT

In spite of the potential advantages of adsorptive separation, it did not achieve wide commercial acceptance until the introduction of the UOP Sorbex process in the early 1960s. Prior to the Sorbex process, adsorptive processes were designed much as laboratory chromatographs. Feed was introduced in pulses, and the composition of products varied with time. Integrating such an intermittent process with continuous processes operating both upstream and downstream was difficult. The Sorbex process, for the first time, offered a truly continuous adsorptive separation process that produced products with essentially constant compositions. The easiest way to understand the Sorbex process is to think of it as a countercurrent flow of liquid feed and solid adsorbent (Fig. 10.3.1). For simplicity, assume the feed is a binary mixture of components A and B, and the adsorbent has a selective attraction for component A. In practice, the feed to a Sorbex unit may contain a multitude of components from which one or more components would be selectively recovered. The positions of injection and withdrawal of the four net streams divide the adsorbent bed in four zones:

Zone 1: adsorption of component A. This zone is between the point of feed injection and raffinate withdrawal. As the feed flows down through zone 1, countercurrent to the solid adsorbent flowing upward, component A is selectively adsorbed from the feed into the pores of the adsorbent. At the same time, the desorbent (component D) is desorbed from the pores of the adsorbent to the liquid stream to make room for A in the pores. Zone 2: desorption of component B. This zone is between the point of feed injection and extract withdrawal. At the fresh-feed point, the upward-flowing solid adsorbent contains the quantity of component A that was adsorbed in zone 1. However, the pores will also contain a large amount of component B, because the adsorbent has just been in contact with fresh feed. The liquid entering the top of zone 2 contains no B, only A and D.

FIGURE 10.3.1 Moving-bed analogy.

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UOP SORBEX FAMILY OF TECHNOLOGIES 10.32

SEPARATION PROCESSES

Thus, B is gradually displaced from the pores by A and D as the adsorbent moves up through zone 2. At the top of zone 2, the pores of the adsorbent contain only A and D. Zone 3: desorption of component A. This zone is between the point of desorbent injection and extract withdrawal. The adsorbent entering zone 3 carries only components A and D. The liquid entering the top of the zone consists of pure D. As the liquid stream flows downward, component A in the pores is displaced by D. A portion of the liquid leaving the bottom of zone 3 is withdrawn as extract; the remainder flows downstream into zone 2 as reflux. Zone 4: isolation zone. The main purpose of zone 4 is to segregate the feed components in zone 1 from the extract in zone 3. At the top of zone 3, the adsorbent pores are completely filled with component D. The liquid entering the top of zone 4 consists of B and D. Properly regulating the flow rate of zone 4 prevents the flow of component B into zone 3 and avoids contamination of the extract. Zone 4: isolation zone. The main purpose of zone 4 is to segregate the feed components in zone 1 from the extract in zone 3. At the top of zone 3, the adsorbent pores are completely filled with component D. The liquid entering the top of zone 4 consists of B and D. Properly regulating the flow rate of zone 4 prevents the flow of component B into zone 3 and avoids contamination of the extract.

The desorbent liquid must have a boiling point significantly different from those of the feed components. In addition, the desorbent must be capable of displacing the feed components from the pores of the adsorbent. Conversely, the feed components must be able to displace the desorbent from the adsorbent pores. Thus, the chosen desorbent must be able to compete with the feed components for any available active pore space in the solid adsorbent solely on the basis of concentration gradients.

DESCRIPTION OF THE PROCESS FLOW

In practice, actually moving a solid bed of adsorbent is difficult. The biggest problem in commercial-size units is ensuring uniform plug flow across large-diameter vessels while minimizing axial mixing. In the Sorbex process, the countercurrent flow of liquid feed and solid adsorbent is accomplished without physical movement of the solid. Instead, countercurrent flow is simulated by periodically changing the points of liquid injection and withdrawal along a stationary bed of solid adsorbent. In this simulated moving-bed technique, the concentration profile shown in Fig. 10.3.1 actually moves down the adsorbent chamber. As the concentration profile moves, the points of injection and withdrawal of the net streams to the adsorbent chamber are moved along with it. A simplified flow diagram for a typical Sorbex unit is shown in Fig. 10.3.2. The separation takes place in the adsorbent chamber, which is divided into a number of adsorbent beds. Each bed of adsorbent is supported from below by a specialized grid that also contains a highly engineered flow distributor. Each flow distributor is connected to the rotary valve by a bed line. The flow distributors between each adsorbent bed are used to inject or withdraw liquid from the chamber or to simply redistribute the liquid over the cross-sectional area of the adsorbent chamber. The numbers of adsorbent beds and bed lines vary with the Sorbex application. In the Sorbex process, four major streams are distributed to and from the adsorbent chamber by the rotary valve. These net streams include

Feed in: raw mixture of all feed components

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FIGURE 10.3.2 Sorbex flow diagram.

Dilute extract out: selectively adsorbed component or components diluted with desorbent Dilute raffinate out: rejected components diluted with desorbent Desorbent in: recycle desorbent from the fractionation section

At any given time, only four of the bed lines are actively carrying the net streams into and out of the adsorbent chamber. The movement of the net streams along the adsorbent chamber is effected by a unique rotary valve, specifically developed by UOP for the Sorbex process. Although, in principle, this switching action could be duplicated with a large number of separate on/off control valves, the UOP rotary valve simplifies the operation of the Sorbex unit and improves reliability. Functionally, the adsorbent chamber has no top or bottom. A pumparound pump is used to circulate process liquid from the last adsorbent bed at the bottom of the adsorbent chamber to the first bed at the top of the chamber. The concentration profile in the adsorbent chamber moves smoothly down past the last bed, through the pump, and back into the first bed. The actual liquid flow rate within each of the four zones is different because the rate of addition or withdrawal of each net stream is different. As the concentration profile moves down the adsorbent chamber, the zones also move down the chamber. The overall liquid circulation rate is controlled by the pumparound pump. This pump operates at four different flow rates, depending on which zone is passing through the pump. The dilute extraction from the rotary valve is sent to the extract column for separation of the extract from the desorbent. The dilute raffinate from the rotary valve is sent to the raffinate column for separation of the raffinate from the desorbent. The desorbent from the bottom of both the extract and raffinate columns is recycled to the adsorbent chamber through the rotary valve.

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UOP SORBEX FAMILY OF TECHNOLOGIES 10.34

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COMPARISON WITH FIXED-BED ADSORPTION

Comparing the characteristics of continuous Sorbex operation with the batch operation of conventional liquid chromatography is interesting. In a conventional chromatographic separation (Fig. 10.3.3), pulses of feed and desorbent are alternately charged to a fixed bed of adsorbent. Once again, assume that the feed is a binary mixture of components A and B. As the feed components move through the adsorbent bed, they gradually separate as the less strongly adsorbed component B moves faster than the more strongly adsorbed component A. A second pulse of feed must be delayed long enough to ensure that the fast-moving band of component B from the second pulse does not overtake the slow-moving band of component A from the first pulse. A mathematical comparison of the Sorbex process with batch chromatography has shown that the batch operation requires 3 to 4 times more adsorbent inventory than the Sorbex process does and twice as much circulation of desorbent. This large difference in adsorbent requirement can be explained in physical terms without going into the details of the mathematical analysis. In the Sorbex process, every portion of the adsorbent bed is performing a useful function at all times. In batch chromatography, portions of the adsorbent bed at various times perform no useful function. This situation is most clearly seen near the entrance of the batch chromatograph. As feed enters the adsorbent bed, the adsorbent near the entrance rapidly comes to complete equilibrium with the feed. As feed continues to enter, this section of the adsorbent serves no purpose other than to convey feed farther down into the bed. A similar situation occurs when desorbent is introduced. Other nonproductive zones exist within the adsorbent bed, between pulses of feed, where excess desorbent is required to keep the bands of component B from overtaking the bands of component A.

FIGURE 10.3.3

Batch absorption.

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UOP SORBEX FAMILY OF TECHNOLOGIES

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10.35

COMMERCIAL EXPERIENCE
Invented by UOP in the 1960s, the Sorbex technique was the first large-scale commercial application of continuous adsorptive separation. The first commercial Sorbex unit, a Molex unit for the separation of linear paraffins, came on-stream in 1964. The first commercial Parex unit came on-stream in 1971. UOP has licensed more than 130 Sorbex units throughout the world, including 78 Parex units, 6 MX Sorbex units, 37 Molex units, 6 Olex units, 5 Sarex units, 1 Cresex unit, and 1 Cymex unit. Most applications of the Sorbex process deliver high-purity products that can be sold or used in downstream technologies. For example, para-xylene is produced directly at 99.9 percent purity at very high recovery and can be oxidized directly to produce purified terephthalic acid (PTA). The C10-C13 nparaffins are produced at 99.5 percent purity and converted to linear olefins as precursors to biodegradable detergents. However, there are some applications in which the design of the Sorbex process can be simplified. One example is the UOP Hysorb* process which is used for producing a concentrated para-xylene stream from mixed xylenes. This concentrated stream can then be fed directly to a single-stage crystallizer for recovery of highpurity para-xylene. This type of application is useful in debottlenecking multistage crystallizers whose recovery is limited by eutectic compositions. Another simplified Sorbex design is the UOP Gasoline Molex* process. This technology is used for recovery of C5 and C6 n-paraffins from light naphtha. The extract can be processed in a Penex unit,* which can isomerize the n-paraffins to their high-octane branched counterparts.

BIBLIOGRAPHY
1. Gembicki, S. A., J. A. Johnson, A. R. Oroskar, and J. E. Rekoske: Adsorption, Liquid Separation, Kirk-Othmer Encyclopedia of Chemical Technology, Wiley, 2002. 2. Johnson, J. A.: Sorbex: Continuing Innovation in Liquid Phase Adsorption, Advanced Study Institute on Adsorption, Vimeiro, Portugal, July 1988. 3. Johnson, J. A., and A. R. Oroskar: Sorbex Technology for Industrial-Scale Separations, International Symposium on Zeolites as Catalysts, Sorbents, and Detergent Builders, Wurzburg, Germany, September 1988. 4. Johnson, J. A., and H. A. Zinnen: Sorbex: A Commercially Proven Route to High Purity Chemicals, Proc. Royal Swedish Academy of Engineering Sciences Symposium, Stockholm, March 1987. 5. Kulprathipanja, S., and J. A. Johnson: Handbook of Porous Solids, Chapter 6.4, Liquid Separations, J. Weitkamp (ed.), Wiley-VCH, Weinheim, Germany, 2001. 6. Millard, M. T., J. A. Johnson, and R. G. Kabza: Sorbex: A Versatile Tool for Novel Separations, UOP Technology Conferences, various locations, September 1988.

*Trademark and/or service mark of UOP.

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UOP SORBEX FAMILY OF TECHNOLOGIES

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