Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 10.6

KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

Stephen W. Sohn
UOP LLC Des Plaines, Illinois

The straight-chain normal paraffins in the kerosene range (C10 to C18) have their principal uses in detergent manufacture, chlorinated fire retardants, plasticizers, alcohols, fatty acids, and synthetic proteins. The separation of these straight-chain normal paraffins from other classes of hydrocarbons, such as branched-chain isoparaffins, naphthenes, and aromatics, was a virtual impossibility prior to the advent of the synthetic zeolites known as molecular sieves. These uniform, molecular-pore-sized adsorbents, developed by Union Carbide in the early 1950s, opened the way for refiners and petrochemical producers to add adsorption as a means of separating hydrocarbon classes to those already known, such as distillation and liquid-liquid extraction. To date, eight kerosene IsoSiv systems have been started up (Table 10.6.1). The IsoSiv* process is licensed by UOP* subsequent to the joint venture ownership of UOP by Union Carbide and Allied Signal in 1988. Currently as a result of the merger of UCC with Dow, and Allied Signal with Honeywell, UOP is now owned jointly by Dow and Honeywell.

GENERAL PROCESS DESCRIPTION

The IsoSiv process separates normal paraffins from a hydrocarbon mixture, such as kerosene or gas oil, by selective adsorption on a molecular-sieve adsorbent material. This material is a crystalline zeolite having uniform pore dimensions of the same order of magnitude as the size of individual hydrocarbon molecules. The molecular sieve used for normal paraffin separation has openings in the crystalline structure that are sized to allow normal paraffin molecules to pass through the pore openings into the internal crystal cavity, where they are retained. Nonnormal hydrocarbons, such as isoparaffins, naphthenes, and aromatics, have larger molecular diameters and are therefore excluded from entering the crystal cavity through the pore opening.
*Trademark and/or service mark of UOP.

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KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS 10.70 TABLE 10.6.1 Unit 1 2 3 4 5 6 7 8
SEPARATION PROCESSES

Kerosene IsoSiv Commercial Applications Start-up 1964 1971 1972 1973 1974 1976 1983 1992 Location United States West Germany Italy Italy Italy Italy Brazil Peoples Republic of China Normal paraffin capacity, BPSD 2300 650 2600 2600 5800 5800 2600 950

Feed type Kerosene Kerosene Kerosene-gas oil Kerosene Kerosene-gas oil Kerosene-gas oil Kerosene Kerosene

Note: BPSD

barrels per stream-day.

The heart of the IsoSiv process is the adsorber section, consisting of vessels filled with molecular-sieve adsorbent. The kerosene or gas oil feedstock is fed into one end of an adsorber vessel, the normal paraffins in the feedstock remain in the vessel by being adsorbed in the molecular sieve, and the remainder of the feedstock passes out the other end of the vessel as a denormalized kerosene gas oil. The normal paraffins are recovered from the adsorber vessel as a separate product by using a purged material. All process hardware in an IsoSiv unit is conventional refinery equipment, such as pumps, furnaces, heat exchangers, and compressors, designed to deliver the feedstock and the purge material to the adsorber section and to remove the products from the adsorber section. The kerosene IsoSiv process typically recovers 95 wt % of the normal paraffins in the feedstock and produces a normal paraffin product of 98.5 wt % purity.

PROCESS PERSPECTIVE
During the early 1960s, the appeal of molecular-sieve adsorption led to widespread efforts at innovating new adsorption technology. Many of these efforts were successful, in that they resulted in molecular-sieve processes capable of separating long-chain normal paraffins from kerosene-range feedstocks at just the time when the detergent industry decided to switch to linear alkylbenzene sulfonates as a basis for its formulations of soft detergents. The consequent demand for long-chain normal paraffins led to a worldwide wave of construction: at least 12 adsorption plants were built to process kerosene-range feedstocks and use processes developed by Union Carbide, UOP, Esso, British Petroleum, Shell, and Texaco. Among the first units was the South Hampton Companys naphtha IsoSiv unit, which was converted to the kerosene range in 1961. In 1964 Union Carbide Corporation installed at its Texas City, Texas, petrochemical complex an IsoSiv unit producing 100,000 metric tons/year (MTA) (220,000 lb/yr) of normal paraffins from kerosene. This unit was to remain the worlds largest normal paraffin-producing plant for almost 10 years. At the beginning of the 1970s, a further extension of adsorption technology was required. The normal paraffins used as substrates for protein production extend into the gas oil feedstock range. Suitable modifications can and have been made to existing adsorption technology to allow successful application to the new requirements. In 1972, Liquichimica S.p.A., now Condea Augusta S.p.A. but then a subsidiary of the Liquigas Group of Italy, installed and started up in Augusta, Sicily, a modified IsoSiv unit to produce 110,000 MTA (242,000 lb/yr) of normal paraffins from both kerosene and gas oil feedstocks. Plant expansions put on-stream in 1973 brought normal paraffin production capacity at Augusta

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KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

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up to approximately 250,000 MTA (551,000 lb/yr), making it by a wide margin the largest single normal paraffin-producing installation in the world. A second unit that came onstream in December 1974 almost doubled previous capacity. A third IsoSiv unit of more than 200,000 MTA (440,000 lb/yr) came on-stream in 1976. Total installed capacity is more than 650,000 MTA (4,862,000 lb/yr) of normal paraffin production. These units have used feedstocks ranging from kerosene to gas oil and intermediate mixtures of both. A seventh kerosene IsoSiv unit came on-line in Brazil in 1983. An eighth came on-line in China in 1992.

DETAILED PROCESS DESCRIPTION

The kerosene IsoSiv process employs the highly selective adsorption capability of molecular sieves. The simplified process flow scheme is shown in Fig. 10.6.1. The basic cycle consists of three steps: adsorption, copurge, and desorption. This section describes each in detail.

Adsorption Step Hydrocarbon feed at elevated temperature and slightly above atmospheric pressure is passed upward through an adsorber vessel, where the normal paraffins are selectively adsorbed in the bed. In processing gas oil feedstock, hexane is added to the gas oil feed to dilute it and prevent capillary condensation from occurring on the adsorbent bed. As the normal paraffins are adsorbed, the liberated heat of adsorption creates a temperature front that travels through the bed. This front closely coincides with the mass-transfer front and gives an indication of when the adsorption step should be terminated to prevent the normal paraffins from breaking through the effluent end of the bed. The temperature front is

FIGURE 10.6.1

Kerosene IsoSiv process.

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KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS 10.72

SEPARATION PROCESSES

used in pilot-plant work to determine optimum design conditions and can be employed in commercial units to set the cycle timer to prevent the front from reaching the bed exit. The unadsorbed isomer and cyclic hydrocarbons and some purge hexane that pass through the beds combine with the copurge effluent and are heat-exchanged against the feed stream to recover heat. This stream is then sent to a distillation system, where the hexane purge material is recovered as a distillate product and the heavier isomers are taken as bottoms products.

Copurge Step After the adsorption step, the normal paraffin-loaded beds are purged in the cocurrent direction with just enough vaporized hexane to displace the nonadsorbed feed and isomeric hydrocarbons from the void spaces in the adsorber vessel. This step is important especially in the production of protein substrates because it ensures that a high-purity product will be recovered from the desorption step. The effluent from the cocurrent purge step is combined with the adsorption effluent stream, as mentioned previously.

Desorption-Purge Step After the copurge step, the beds are purged countercurrently with hexane. This countercurrent purging desorbs the normal paraffins and sweeps these desorbed vapors from the bed, thus maintaining the average desorbate partial pressure below the value in equilibrium with the loading on the bed. The continuous removal of the desorbate vapor and the simultaneous transfer of the adsorbed phase to the purge gas in an attempt to establish equilibrium drive the desorption toward completion. In addition to this stripping effect, the normal hexane itself becomes adsorbed on the bed and helps displace the heavier normal paraffin desorbate. A complete removal of the heavy normal paraffin adsorbate is not achieved on each desorption. An economic balance between the bed size, as determined by the fraction of heavy normal adsorbate removed (or delta loading), and the hexane purge required determines the degree of removal of the heavy normals obtained. As the purge quantity is decreased, the delta loading is decreased; and larger adsorbers are required for a given hydrocarbon feed throughput and cycle time. This decreased delta loading increases the rate of adsorbent deactivation and consequently the required burn-off frequency because the higher residual loading increases the rate of coke formation. Conversely, increasing the purge quantity increases delta loading until the hexane-handling equipment and operating costs become significant factors. The desorption effluent containing heavy normal paraffins and hexane is partially condensed by heat exchange with the cold hexane purge. The vapor fraction and the condensate are transferred to the normal dehexanizer system, where the normal paraffins are separated from the hexane by standard fractionating techniques. The normal paraffin product from the bottom of the column is cooled and removed from the process. This separation is relatively easy because of the wide difference in boiling point between hexane and the lightest heavy normal paraffin. The recovered hexane from this column is also condensed and circulated back to the hexane accumulator without fractionation. Small additions of fresh hexane are required to make up losses of hexane carried out in both product streams. The foregoing operation sequence is integrated into continuous processing by the cyclic use of several adsorber vessels. Automatic valves are operated by a sequencing control system. The flow of both feed and products is uninterrupted. Suitable interlocks and alarms are provided so that the plant can operate with a minimum of operator attendance.

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KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS

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Oxidative-Regeneration Description As the adsorber beds are cycled at the elevated operating temperatures, a carbonaceous deposit gradually accumulates. This deposit reduces the capacity of the adsorbent, and this reduction ultimately results in a breakthrough of normal paraffins into the isomer product stream and decreased normal paraffin recovery. The rate at which this deposit accumulates depends on factors such as temperature, feed impurities, feed properties, cycle time, and residual paraffin loadings. This type of adsorbent deactivation is not permanent, and the original bed capacity can be restored by burning off this deposit under controlled conditions. For a kerosene-type feedstock, a bed can be cycled for 15 to 30 days before oxidative regeneration is necessary. For a gas oil feedstock, the period is reduced to about 6 to 10 days. When a bed has been cycled to the point at which oxidative regeneration is required, it is removed from the processing operation, and another adsorber vessel is put into operation. This change is made without any interruption in the cycling sequence. The coked bed is removed from cycling after the desorption step and is given an additional long desorption purge to remove as much of the residual normal paraffins as possible. The bed is then completely isolated from the cycling system, and a downflow circulation of nitrogen is pumped by means of a compressor or blower and then passed through a heater to the adsorber vessel. The circulation of hot nitrogen has two purposes: to purge the hexane from the bed and to raise the temperature of the bed to above the coke ignition point prior to the introduction of oxygen into the system. The effluent gas from the bed is cooled to condense the hydrocarbons and water that desorb. When the bed is up to temperature, air is introduced into the circulating stream at a controlled rate. The oxygen in the gas combusts with coke in the top of the bed. The heat released from combustion is carried out of the burning zone as a preheat front traveling ahead of the burning front. This preheat front raises the bed temperature even further. This temperature is controlled by regulating the amount of oxygen in the entering gas. Because excessive internal adsorbent temperatures permanently destroy the molecular-sieve crystal, the gas-phase temperature is critical. As the burning front passes through the bed, the temperature drops back to the gas inlet temperature. Because the coke deposit contains hydrogen, water is formed during combustion in addition to carbon oxides. This water must be removed from the system because the molecular-sieve crystal is permanently damaged by repeated exposure to water at high temperatures. To minimize this damage, a dryer is used to prevent the water from accumulating. The proper design of the regeneration process and the rugged nature of the molecular sieve ensure that the adsorbent has a long operating life. After the regeneration is complete, the bed is cooled down to the process operating temperature and purged of any remaining oxygen by circulating nitrogen. The bed is now ready to go on-stream to replace one of the adsorbers in use so that it, in turn, can be reactivated.

WASTE AND EMISSIONS

During normal operation of the kerosene IsoSiv unit, the vent gas is not expected to contain more than 5000 vol ppm of total sulfur on the average. The maximum peak sulfur level in the vent gas stream is not expected to exceed 5 vol % when the unit is operating with feedstocks containing up to 500 wt ppm total sulfur. A second vent stream contains approximately 1000 vol ppm of sulfur during the burn-off of an adsorber bed. The peak concentration is not expected to exceed 5 percent. This vent will also contain approximately 2 vol % carbon monoxide.

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KEROSENE ISOSIV PROCESS FOR PRODUCTION OF NORMAL PARAFFINS 10.74

SEPARATION PROCESSES

Proper handling of these vent gas streams depends on many factors. One suggested method of handling these streams is to feed them to the hexane-heater firebox, provided acceptable stack sulfur levels can still be maintained.

ECONOMICS
Many factors affect the cost of extracting normal paraffins. They include the nature of the feedstock from which the normal paraffins are to be extracted, the specifications of the product normal paraffins, the production capacity or size of the plant, and the location. The last factor includes such items as climatic conditions and availability and cost of labor, utilities, storage, and transportation. The feedstock is of primary importance. The normal paraffin content of gas oils ranges from 10 to 40 percent, depending on the crude oil source. The higher the normal paraffin content, the more amenable it is for normal paraffin processing. Refiners also find this feed the least attractive for fuel oil or diesel fuel because of its high pour or freeze points. Extracting the normal paraffins reduces the freeze point considerably, thus making the isomer product more salable. Impurities such as the amount of sulfur must also be considered. Normal paraffin specifications as required by the selected fermentation process are also important. The hydrocarbon range, normal paraffin content, and types of impurities bear directly on whether prefractionation of the feedstock before normal paraffin extraction or postfractionation after extraction is required and on whether and to what degree some form of posttreatment is required to remove trace sulfur and aromatic compounds. The IsoSiv process produces normal paraffins at 98.5 wt % purity. Plant size is important because large plants tend to be more economical. For normal paraffin extraction, plants producing less than 100,000 MTA (220,000 lb/yr) are considered to be relatively small from an economic point of view. However, plants with capacities larger than 500,000 MTA (1,102,000 lb/yr) offer little economic incentive. Location is also important. All these economic considerations, plus an uncertain and rapidly changing economic climate, make estimates of capital investment and operating costs for extracting normal paraffins extremely tenuous. However, the estimated erected cost of a kerosene IsoSiv unit for the recovery of 100,000 MTA (220 million lb/yr) of normal paraffins is about $30 million. In summary, commercially proven large-scale production technology is available for the economic production of high-quality normal paraffins in the kerosene range. The utility requirements for such a unit per metric ton of product are as follows: Electric power, kWh Hot oil heat, 103 J/h (Btu/h) Cooling water circulated [15C (27F) rise], m3 (gal) 79.5 205 (195) 8.3 (293)

BIBLIOGRAPHY
LaPlante, L. J., and M. F. Symoniak: Heres One Way of Economically Producing Long-Chain Paraffins, NPRA Meeting, San Antonio, Tex., 1970. Reber, R. A., and M. F. Symoniak: IsoSiv: A Separation Process to Product n-Paraffins for Single Cell Protein, American Chemical Society meeting, Philadelphia, April 1975.

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