Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 5.2

UOP PACOL DEHYDROGENATION PROCESS

Peter R. Pujad
UOP LLC Des Plaines, Illinois

INTRODUCTION
Paraffins can be selectively dehydrogenated to the corresponding monoolefins by using suitable dehydrogenation catalysts. Iron catalysts have long been used for the dehydrogenation of ethylbenzene to styrene, and catalysts made of chromia (chrome oxide) supported on alumina have long been used for the dehydrogenation of light paraffins (for example, n-butane to n-butene) and the deeper dehydrogenation of olefins to diolefins (for example, n-butene to 1,3-butadiene). However, newer commercial processes for the dehydrogenation of light and heavy paraffins are based on the use of noble-metal catalysts because of the superior stability and selectivity of these catalyst systems. In the late 1940s and through the 1950s, the pioneering work done at UOP* by Vladimir Haensel on platinum catalysis for the catalytic reforming of naphthas for the production of high-octane gasolines and high-purity aromatics showed that platinum catalysts have interesting dehydrogenation functions. This research area was later pursued by Herman Bloch and others also within UOP. In 1963-64, UOP started development work on heterogeneous platinum catalysts supported on an alumina base for the dehydrogenation of heavy n-paraffins. The resulting successful process, known as the Pacol* process (for paraffin conversion to olefins), was first commercialized in 1968. The advent of the UOP Pacol process marked a substantial transformation in the detergent industry and contributed to the widespread use of linear alkylbenzene sulfonate (LAS or LABS) on an economical, cost-effective basis. As of mid-2003, more than 40 Pacol units have been built, or are under design or construction; practically all new linear alkylbenzene (LAB) capacity built on a worldwide basis over the last two decades makes use of UOPs Pacol catalytic dehydrogenation process. Maintaining technological superiority over some 30-odd years requires continued innovation and improvement, principally of the dehydrogenation catalyst, the reactor design, and operating conditions because these have the greatest impact on the overall process economics. The first commercial Pacol dehydrogenation catalysts, denoted DeH-3 and DeH*Trademark and/or service mark of UOP.

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UOP PACOL DEHYDROGENATION PROCESS 5.12

DEHYDROGENATION

4, came on-stream in the mid-1960s. They were soon superseded by a newer catalyst, DeH5, that was commercialized in 1971 and dominated the market for several years. In 1983, DeH-7 catalyst was introduced. This new catalyst exhibited about 1.75 times the stability of its predecessor, DeH-5, and soon replaced it as the dominant Pacol catalyst. Development efforts continued, and in 1998, DeH-11 was commercialized. This catalyst is the first layered sphere catalyst to be offered by UOP in which a thin reactive layer is coated onto an inert one. The result is an advantage in selectivity to mono-olefins. In 2001 DeH-201 was introduced. This catalyst, also a layered sphere, allows for higher conversion operation than previous Pacol catalysts. All these various generations of paraffin dehydrogenation catalysts have resulted in improved yields at higher conversion and higher operating severities, thus allowing for smaller and more economical units for a given production capacity. Since 1980, UOP has adapted similar catalysts to the selective catalytic dehydrogenation of light olefins (propane to propylene and isobutane to isobutylene) in the Oleflex* process; a number of large-capacity units have been built for this application. Because of the higher severity, light paraffin dehydrogenation units make use of UOPs proprietary CCR* continuous catalyst regeneration technology, which was originally developed and commercialized for the catalytic reforming of naphthas at high severity. Because the Pacol process operates at a lower severity, catalyst runs are significantly longer, and CCR technology is not needed.

PROCESS DESCRIPTION
The catalytic reaction pathways found in the dehydrogenation of n-paraffins to nmonoolefins [linear internal olefins (LIO)] in addition to other thermal cracking reactions are illustrated in Fig. 5.2.1. A selective catalyst is required if only LIO is to be the main product. In the Pacol reaction mechanism, the conversion of n-paraffins to monoolefins is near equilibrium, and therefore a small but significant amount of diolefins and aromatics is produced. In the alkylation process, the diolefins consume 2 moles of benzene to yield heavier diphenylalkane compounds or form heavier polymers that become part of the heavy alkylate and the bottoms by-products of the hydrofluoric (HF) acid regenerator. Thus,

FIGURE 5.2.1

Dehydrogenation reaction pathways.

*Trademark and/or service mark of UOP.

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UOP PACOL DEHYDROGENATION PROCESS

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5.13

diolefin formation represents a net loss of alkylate yield. In 1984, UOP developed the DeFine* process, a highly selective catalytic hydrogenation process to convert diolefins back to monoolefins. Detergent complexes licensed prior to 1986 included only Pacol and HF Detergent Alkylate* units. The first DeFine unit came on-stream during the fourth quarter of 1986; all subsequent Pacol process units have also incorporated DeFine hydrogenation reactors, and DeFine reactors have also been retrofitted into a growing number of existing older Pacol units. Both Pacol and DeFine processes are also used in the latest process developed and commercialized by UOP, the Detal* process, for the production of LAB using a heterogeneous solid catalyst instead of the older, traditional HF acid catalyst. The dehydrogenation of n-paraffins is an endothermic reaction with a heat of reaction of about 125 kJ/g mol (30 kcal/g mol; 54,000 Btu/lb mol). The equilibrium conversion for the dehydrogenation reaction is determined by temperature, pressure, and hydrogen partial pressure. As expected, the equilibrium conversion increases with temperature and decreases with pressure and with increasing hydrogen-to-hydrocarbon ratio. Kinetically, the overall conversion depends on space velocity (feed-to-catalyst ratio): excessively high space velocities do not allow for sufficient conversions, and space velocities that are too low lead to lower selectivities because of the onset of side and competitive reactions. Figure 5.2.2 illustrates the flow scheme of an integrated complex incorporating Pacol, DeFine, and HF Detergent Alkylate units or Pacol, DeFine, and Detal units. The main differences between the two flow schemes are in the alkylation section as a result of the elimination of the HF acid handling and neutralization facilities; for example, no alumina treater is used in conjunction with a Detal process unit. In the Pacol process, linear paraffins are dehydrogenated to linear olefins in the presence of hydrogen over a selective platinum dehydrogenation catalyst. An adiabatic radial-flow reactor with feed preheat is normally used to compensate for the endothermic temperature drop and to minimize pressure drop within an efficient reactor volume. Relatively high space velocities are used so that only a modest amount of catalyst is required. Hydrogen and some by-product light ends are separated from the dehydrogenation reactor effluent, and a part of this hydrogen gas is recycled back to the dehydrogenation reactor to minimize coking and enhance catalyst stability. The separator

FIGURE 5.2.2

Integrated LAB complex.

*Trademark and/or service mark of UOP.

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UOP PACOL DEHYDROGENATION PROCESS 5.14

DEHYDROGENATION

liquid is an equilibrium mixture of linear olefins and unconverted n-paraffins, which are charged to a DeFine reactor for the selective conversion of diolefins to monoolefins. A near-stoichiometric amount of hydrogen is also charged to the DeFine reactor. The DeFine reactor effluent is stripped to remove dissolved light hydrocarbons. The stripper bottoms, a mixture of monoolefins and unconverted n-paraffins, is then charged together with benzene to the alkylation unit, where benzene is alkylated with the monoolefins to produce LAB. Small amounts of heavy alkylate and, if HF is used, polymer from the acid regenerator bottoms are also formed. Benzene and n-paraffins are fractionated from the alkylation reactor effluent and then recycled to the alkylation and Pacol reactors, respectively. The final column fractionates the LAB product overhead and recovers heavy alkylate as bottoms product. A similar process scheme can be used to produce concentrated n-olefins. Figure 5.2.3 illustrates the flow scheme of an integrated complex featuring the Pacol, DeFine, and Olex* processes. In this combination, the Pacol and DeFine processes are the same as described previously. The stripper bottoms stream, which consists of an equilibrium mixture of n-paraffins and n-monoolefins, is now sent to an Olex separation unit. The Olex process uses continuous liquid-phase, simulated countercurrent adsorptive separation technology to recover high-purity n-olefins out of the mixture. The olefinic extract and the paraffinic raffinate streams that leave the adsorption chamber both contain desorbent. These two streams are fractionated for the removal and recovery of the desorbent, which is then recycled back to the adsorption chamber. The paraffin raffinate is recycled to the Pacol dehydrogenation unit for complete conversion of the unconverted n-paraffins to the ultimate n-olefin product. Table 5.2.1 shows the olefins composition of a typical Olex process. The LIO produced by the Pacol process and recovered in an Olex unit is premium material for the production of detergent alcohols via hydroformylation. Oxo technologies, such as Shells, Exxons (formerly Norsolors and Ugine Kuhlmanns), or Sasols can be used. Three integrated Pacol-Olex-Oxo complexes are currently operating. Surfactants made from detergent alcohols manufactured according to this combination of technologies show superior properties in terms of detergency and solubility.

FIGURE 5.2.3

Integrated detergent olefins complex.

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UOP PACOL DEHYDROGENATION PROCESS

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TABLE 5.2.1 Composition

Typical Olex Extract Composition With PEP, wt % 95.0 3.1 0.5 98.5 98.6 0.2 1.2 100.0 Without PEP, wt % 92.5 3.0 0.5 96.0 96.0 3.0 1.0 100.0

Linear monoolefins Other monoolefins Diolefins Total Olefins Aromatics (see text) Paraffins Total

PACOL PROCESS IMPROVEMENTS

Repeated successful attempts have been made over the years to increase the per-pass conversion of n-paraffins across the Pacol reactor and still preserve a high selectivity and high overall yield of linear olefins. The more severe operating conditions used for higher reactor conversions also result in faster deactivation of the dehydrogenation catalyst. The catalyst used in the Pacol process has a direct impact on the reaction kinetics but not on equilibrium conversion, which is governed by thermodynamic principles. Therefore, most of the process improvements have been associated with modifications in reactor design or in operating conditions. A high-conversion Pacol process was developed partially in response to the significant increase in feedstock and utility costs that occurred between 1974 and 1981. Operating the process at higher per-pass conversions affords several advantages. A smaller combined-feed stream to the dehydrogenation reactor permits a smaller-size unit and results in lower capital investment and utility costs. As the unconverted n-paraffins pass through the alkylation reaction zone and are separated by fractionation for recycle to the Pacol reactor, the reduction in the recycle stream also decreases the capital investment and operating cost of the detergent alkylation unit. All recent units are of the high-conversion type. Criteria for the high-conversion design were to maintain the same selectivity to linear olefins and increase conversion. This approach required changes in operating conditions. Figure 5.2.4 shows the effect of pressure on olefin selectivity at constant temperature and hydrogen-to-feed mole ratio. At lower pressures, higher n-paraffin conversion can be obtained and selectivity can be maintained because of the more favorable dehydrogenation equilibrium. A similar effect can be observed when the hydrogen-to-feed ratio is lowered. The latest designs of the Pacol process take advantage of both of these variables. The net result is a 30 percent increase in n-paraffin conversion compared to the earlier designs. Overall, the Pacol catalyst possesses an attractive catalyst life in terms of metric tons of LAB produced per kilogram of catalyst. A typical run on a single Pacol catalyst load ranges from 30 to 60 days, depending on operating severity. As shown on Fig. 5.2.5, two parallel reactors were used for most units built through 1987. In this design, one reactor operates at any given time and the second reactor is on standby. When the decline in catalyst activity warrants a change, the reactors are switched. To expedite the change and minimize interruption in production, a start-up heater is provided. For safe operation and isolation, each valve shown in the drawing actually represents a double block and bleed valve. Thus, 16 large valves are required on process lines. These valves cycle from cold-to-hot and hotto-cold service at each change of the reactors and require regular maintenance to control

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UOP PACOL DEHYDROGENATION PROCESS 5.16

DEHYDROGENATION

FIGURE 5.2.4 sion.

Effect of pressure on conver-

leakage. To minimize maintenance and simplify the operation, a new reactor design (Fig. 5.2.6) is now used commercially in seven units. This design provides a catalyst hopper on the top and on the bottom of a single reactor and a hydrogen and a nitrogen purge system. When catalyst activity has declined sufficiently, the catalyst from the reactor is withdrawn to the lower hopper, and fresh catalyst is loaded from the top hopper, thereby eliminating the need for valves in large-diameter process lines. An additional catalyst volume inside the reactor vessel is provided as a preheating zone. A portion of the hydrogen-rich recycle gas passes through a heat exchanger and is used for preheating the catalyst. The hydrogen-rich gas is also used to purge hydrocarbons from the catalyst that leaves the reactor. This design is similar in concept to that used commercially in more than 100 UOP CCR Platforming* units. Outside the reactor sector, other process design changes made over the past few years have also contributed to enhancing the reliability and economics of the Pacol process. One, for example, reflects the introduction of rotary screw compressors instead of the reciprocating or centrifugal machines used in earlier Pacol units. Rotary screw compressors are especially effective when lube oil contamination of the process gas cannot be tolerated. Nonlubricated screw compressors can deliver gases with the same reliability as a centrifugal compressor, and the positive displacement of screw compressors makes them well suited for applications that require high compression ratios and large changes in gas molecular weights. In addition, screw machines offer economic benefits over comparable reciprocating machines in terms of lower installation costs and not requiring a spare. Changes in engineering design also resulted in increased energy efficiency, reduced fractionation losses, and improved operational stability. Some of these design changes concerned the Pacol unit itself, but many were more closely associated with the associated downstream units. As in the design of other process units, significant energy savings were achieved by relatively small incremental expenditures in increased exchanger area and by rearrangement of the heat exchanger network. For example, a low-pressure-drop contact condenser was advantageously introduced to cool the reactor effluent after the hot combined-feed effluent exchanger. Also, the application of efficient mixing technology in the reaction zone
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UOP PACOL DEHYDROGENATION PROCESS

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FIGURE 5.2.5

Two-reactor design.

enhanced the quality of the reaction environment and allowed operation with recycle ratios close to their minimums.

YIELD STRUCTURE
If expressed on a weight basis, the yield of linear olefins from n-paraffins in the Pacol process depends on the molecular weight of the feedstock. In the common situation in which linear olefins are produced for the manufacture of LAB, typically from n-paraffins in the C10 to C13 carbon range, about 1.05 kg of feed is required per 1.00 kg of linear olefins, or about 97 percent of the theoretical stoichiometric yield.

COMMERCIAL EXPERIENCE
More than 30 Pacol process units have been built and brought on-stream around the world since the mid-1960s, and practically without exception, all are still operating. A few other units are in various stages of design and construction. Most Pacol units are directly integrated with a benzene alkylation unit for the production of LAB without the need for an intermediate separation or recovery of the LIOs. These units represent an aggregate design capacity in excess of 1.3 million metric tons per year (MTA) of LAB; however, through revamps and expansions, the actual operating capacity is significantly larger. In addition, other Pacol units are associated with Olex units to recover LIO for the production of detergent alcohols.

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UOP PACOL DEHYDROGENATION PROCESS 5.18

DEHYDROGENATION

FIGURE 5.2.6

One-reactor design.

PROCESS ECONOMICS
Because a Pacol unit is never found by itself, but is instead integrated with a DeFine unit and either a HF Detergent Alkylate unit, a Detal solid-acid alkylation unit, or an Olex LIO separation unit, the economics can be discussed only in conjunction with the associated units. Details on LAB production can be found in Chap. 1.5. As a different example, economics for the production of 60,000 MTA of LIO starting from n-paraffins are shown in Table 5.2.2. The complex includes Pacol, DeFine, and Olex units and reflects typical economic conditions. The resulting production cost of $617/MT of LIO compares favorably with the costs of production of LIO or LAO by other routes. A typical product composition is shown in Table 5.2.1. If desired, the aromatic content can be reduced by adding the UOP proprietary PEP* (Pacol Enhancement Process) for the selective removal of aromatics; introduction of this novel technology has resulted in more than 90 percent reduction in the aromatic content and a 2.5 to 3.0 percent increase in olefin purity as seen in Table 5.2.1.
*Trademark and/or service mark of UOP.

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UOP PACOL DEHYDROGENATION PROCESS

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TABLE 5.2.2 Economics for LIO Production Using the UOP Pacol, DeFine, and Olex Processes* Per MT of LIO Unit cost, $ Raw materials: n-Paraffins (98% purity) By-product credits Catalysts and chemicals Utilities: Power Steam Cooling water Fuel fired (92% eff.) Labor, maintenance, direct overhead, and supervision Overhead, insurance, property taxes, depreciation, amortization Total cost of production
*Estimated erected cost: $65,000,000 (basis: 60,000 MT/year of LIO). MT

Units 1.05 MT 0.05 MT

$ 420.0 13.1 32.2

400/MT

0.05/kWh 7.1/MT 0.01/m3 2.32/GJ

305 kWh 0.16 MT 17 m3 16.30 GJ

15.3 1.1 0.2 37.8 25.2 98.6 617.3

metric tons.

BIBLIOGRAPHY
Vora, B. V., P. R. Pujad, and M. A. Allawala, Petrochemical Route to Detergent Intermediates, 1988 UOP Technology Conference.

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UOP PACOL DEHYDROGENATION PROCESS

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