Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 8.6

UOP UNISAR PROCESS FOR SATURATION OF AROMATICS

H. W. Gowdy
UOP LLC Des Plaines, Illinois

INTRODUCTION
The UOP* Unisar* process saturates the aromatics in naphtha, kerosene, and diesel feedstocks. The use of highly active noble-metal catalysts permits the reactions to take place at mild conditions. Because of the mild conditions and the very selective catalyst, the yields are high, and hydrogen consumption is largely limited to just the desired reactions. A total of 20 Unisar units have been licensed worldwide. Among the applications of the Unisar process are smoke-point improvement in aircraft turbine fuels, reduction of the aromatic content of solvent stocks to meet requirements for air pollution control, production of cyclohexane from benzene, and cetane number improvement in diesel fuels. The Unisar process also produces low-aromatics diesel with excellent color and color stability. This process was first applied to upgrading solvent naphthas and turbine fuel. The first commercial Unisar plant, a unit processing 250,000 metric tons per year (MTA) [6000 barrels per stream day (BPSD)] was built in Beaumont, Texas, and went on-stream early in 1969. It was designed to saturate the aromatics in untreated straight-run solvent naphtha containing 100 wt ppm sulfur. The aromatics were reduced from 15 to 1.0 vol %. The first catalyst cycle lasted more than 8 years. Another of the early plants was started up at Unocals San Francisco Refinery in 1971. This unit, which processes 600,000 MTA (14,500 BPSD), reduces the aromatics in hydrocracked turbine stock from 30 wt % to less than 4 wt %. During a test at the latter unit, the aromatics were reduced from 29 wt % to less than 0.1 wt %.

APPLICATION TO DIESEL FUELS

In the 1990s, the need to increase the cetane number of diesel fuel has grown. Increasing the cetane number improves engine performance and decreases emissions. Cetane num*Trademark and/or service mark of UOP.

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UOP UNISAR PROCESS FOR SATURATION OF AROMATICS 8.60

HYDROTREATING

ber is a strong function of hydrocarbon type and number of carbon atoms. Figure 8.6.1 plots cetane number versus number of carbon atoms for compounds in the diesel boiling range. The graph shows that normal paraffins have the highest cetane number, which increases with chain length. Isoparaffins and mononaphthenes with side chains are intermediate in cetane number, and polynaphthenes and polyaromatics have the lowest cetane numbers. The saturation of aromatics in diesel-range feeds leads to an increase in cetane number (Fig. 8.6.2). However, whether this reaction alone is sufficient to reach cetane numbers near 50, as required in some European countries, depends on the overall compound distribution in each feed. One version of the advanced Unisar catalyst described later in this chapter has built into it some hydrocracking activity to promote naphthenic ring opening and upgrade these low-cetane feedstocks. These diesel-range feeds typically have substantially higher boiling points and much higher levels of nitrogen and sulfur than the lighter kerosene and solvent feedstocks for which the original Unisar process was developed. The original noble-metal catalysts used for the Unisar process have limited tolerance to the nitrogen and sulfur contaminants in diesel-range feeds. Thus, new catalysts have been developed to effectively treat these more difficult feeds. In addition, these feeds must be substantially hydrotreated to remove sulfur and nitrogen before they can be treated with the noble-metal Unisar catalysts. A flow scheme that integrates the hydrotreating and aromatics-saturation stages has been developed so that low-sulfur, high-cetane diesel fuels can be efficiently produced.

104

n-P ara

96 88 80 72 Cetane Number

ffi
ns efi Ol

ns

af fin

64 56 48 40 32
Aromati

op

Is

on

yc oc

lon

ar

24 16 8 0 0 8

ns s ali ene etr T hal pht Na

cs

12

th ph

en

es

Decalins

16

20

24

28

No. of Carbon Atoms

FIGURE 8.6.1 Cetane number versus hydrocarbon type.

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UOP UNISAR PROCESS FOR SATURATION OF AROMATICS

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8.61

FIGURE 8.6.2 Typical aromatics-cetane relationship.

PROCESS DESCRIPTION
The UOP Unisar process is carried out at moderate temperatures and pressures over a fixed catalyst bed in which aromatics are saturated in a hydrogen atmosphere. Exact process conditions vary, depending on the feedstock properties and the level of aromatics desired in the product.

Chemistry The primary reaction in the Unisar process is the hydrogenation of aromatics. Other reactions that occur are hydrogenation of olefins, naphthenic ring opening, and removal of sulfur and nitrogen. At conditions that result in significant aromatics hydrogenation, olefins in the feed are completely hydrogenated. When the concentrations of sulfur and nitrogen in the feed are relatively high, the hydrogenation of aromatics is severely limited until the concentrations of heterocompounds have been greatly reduced. The overall aromatics-saturation reaction rate increases with increases in aromatics concentration, hydrogen partial pressure, and temperature. The reaction rate decreases with increases in the concentration of sulfur and nitrogen compounds and the approach to equilibrium. At low temperatures, aromatics in the product are reduced by increasing the temperature. At these low temperatures, reaction kinetics control the aromatics conversion. However, as temperatures are further increased, a point is reached at which additional temperature increases actually increase aromatics in the product (Fig. 8.6.3). Above this temperature, the reverse dehydrogenation reaction has become dominant, and aromatics conversion is controlled by chemical reaction equilibrium. Thus, using highly active catalysts is important so that lower temperaturesthat is, temperatures that are farther from the equilibrium limitationcan be used. Naphthalene and tetralin have been used as a model to study the reaction mechanism for saturation of diaromatics with the Unisar noble-metal catalyst. The saturation of naphthalene to tetralin and of tetralin to decalin both fit first-order kinetics quite well. However, when these rate constants were used together in a sequential mechanism in which naphthalene is saturated to tetralin and the tetralin is then saturated to decalin, the resultant calculated product distribution did not fit the distribution observed experimentally.

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UOP UNISAR PROCESS FOR SATURATION OF AROMATICS 8.62

HYDROTREATING

FIGURE 8.6.3

Temperature effect on diesel aromatics reduction.

When the simultaneous saturation of both the naphthalene rings to yield decalin directly is considered along with the saturation of each ring sequentially, the experimental yield distribution can be reproduced satisfactorily. Furthermore, the reaction leading to the simultaneous saturation of both rings of naphthalene to yield decalin directly without the intermediate formation of tetralin is significantly faster than the saturation of only one ring to yield the intermediate tetralin. The Unisar catalyst study also showed that the overall rate of naphthalene saturation that is, the sum of the rates of both saturation reactionsis approximately twice as fast as the saturation of tetralin. This result conforms to the generally accepted concept that diaromatics undergo saturation more readily than monoaromatics.

Catalysts The Unisar catalysts are composed of noble metals on either an amorphous or molecularsieve support. The original AS-100* catalyst was developed for kerosene and naphtha solvent hydrogenation. It is highly active and stable in this service. For example, the Unisar plant at the Unocal San Francisco refinery saturates aromatics in the kerosene cut from the hydrocracker to increase the smoke point. This catalyst was loaded in 1971. The original load is still in the reactors, and it has not been regenerated. The new AS-250 catalyst was specifically developed to treat diesel feedstocks. The catalyst has greatly improved tolerance to the organic sulfur and nitrogen compounds present in diesel-range feeds and much higher activity and stability when treating these feeds. The AS-250 catalyst is 65C (150F) more active that its predecessor. This higher activity allows for a more economic Unionfining* design as a result of lower design pressure and higher space velocity. The nitrogen and sulfur tolerance of the AS-250 catalyst was demonstrated in a 200day pilot-plant stability text. The base feed for the study was a 382C (720F) endpoint heavy diesel hydrotreated to 50 wt ppm sulfur and 20 wt ppm nitrogen. After more than a

*Trademark and/or service mark of UOP.

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UOP UNISAR PROCESS FOR SATURATION OF AROMATICS

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month on-stream, a feed containing 450 wt pm sulfur and 135 wt ppm nitrogen was fed to the unit for 24 hours, and then the base feed was returned to the unit. The AS-250 catalyst showed no permanent activity loss or increase in deactivation rate. Some hydrocracking activity has been built into the AS-250 catalyst to allow naphthenic ring opening to upgrade low-cetane feedstocks. This catalyst delivers high distillate yields, and the converted material is essentially all naphtha.

Typical Process Conditions The Unisar reactor conditions depend on the feed properties and on the level of aromatics saturation required. Typical operating conditions for commercial Unisar units are Space velocity: 1.0 to 5.0 vol/vol h Pressure range: 3500 to 8275 kPa (500 to 1200 lb/in2 gage) Recycle gas H2 purity: 70 to 90 mol % Recycle gas rate: 3000 to 6000 standard cubic feet per barrel (SCFB) Temperature range: 205 to 370C (400 to 700F)

Unisar Process Flow A typical Unisar unit can be represented by the flow diagram shown in Fig. 8.6.4. Fresh feed to the unit is combined with recycle gas from the separator and with makeup hydrogen. The mixture of gas and feed is heated by exchange with reactor effluent and by a fired heater before entering the reactor. In the reactor, aromatic compounds are hydrogenated to

FIGURE 8.6.4 Unisar or Unionfining unit.

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UOP UNISAR PROCESS FOR SATURATION OF AROMATICS 8.64

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the corresponding naphthenes, olefins are hydrogenated to paraffins, and any organic sulfur compounds are converted to hydrogen sulfide. Because these catalytic reactions are exothermic, the reactor is divided into multiple catalyst beds that have high-efficiency quench sections in between. In these quench sections, the gas and liquid reactants flowing from the top bed are thoroughly mixed with cold recycle hydrogen to reduce the temperature of the reacting mixture. Then this mixture is distributed over the top of the bed below the quench section. In this way, the temperature is kept in the range necessary for reaction but below the level at which thermodynamic limitations on the reaction rate would be significant. The reactor effluent stream is initially cooled by heat exchange with the reactor feed and then by air before it enters the gas-liquid separator. The separator gas stream may be scrubbed with an amine solution to remove hydrogen sulfide before the gas is recompressed to the reactor. The need for this scrubbing step depends on the amount of sulfur in the feed. The separator liquid flows to a stripping column, where any light ends are removed. The finished Unisar product is withdrawn from the bottom of the stripper. Maximum Quality Distillates (MQD) When the Unisar process is used to saturate aromatics in feedstocks containing substantial amounts of sulfur and nitrogen, the UOP Unionfining process is used first to remove organic sulfur and nitrogen compounds. Then the Unisar process is used to saturate the aromatics in the hydrotreated feed. The generalized flow diagram in Fig. 8.6.4 also represents the Unionfining process. Because the Unionfining and Unisar flow diagrams are so similar, the total capital cost would be double that of the Unionfining plant if Unionfining and Unisar steps were done in separate plants. For this reason, the two steps have been combined into the integrated UnionfiningUnisar process (Fig. 8.6.5). The integrated unit has no pressure letdown between the Unionfining and Unisar reactors. Instead, the Unionfining effluent flows to a stripper, where

FIGURE 8.6.5

Integrated Unionfining and Unisar unit.

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UOP UNISAR PROCESS FOR SATURATION OF AROMATICS

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hydrogen sulfide and ammonia are stripped from the hydrotreated feed by hydrogen. This stripped material is then processed in the Unisar reactor. The integration of these process steps minimizes required equipment, maximizes heat integration, and optimizes utilities. The total cost of this integrated design is just 30 percent more than that of the original Unionfining plant. Some refiners are faced with lower-sulfur regulations in the immediate future, but new cetane and aromatics specifications are not expected to go into effect until a few years later. Taking into consideration the return on investment over time and the tight availability of capital, the optimal solution for these refiners is to build the Unionfining portion of the complex first and add the Unisar section later. Consequently, this design was also done so that the hydrogen stripper and Unisar stage can be easily added later. The Unionfining reactor, fired heater, and all the heat exchangers and separators in the initial Unionfining unit have the same size requirements for both the Unionfining unit alone and the integrated Unionfining-Unisar unit.

PROCESS APPLICATIONS
A total of 20 Unisar units have been licensed worldwide. Some typical commercial applications of the Unisar process are shown in Table 8.6.1. The aromatics in the distillate feed are reduced from 24.6 to less than 1 vol %. The aromatics in the kerosene are reduced from 28.2 to 3.0 vol %, and those in the solvent stock are reduced from 10 to less than 0.5 vol %. An example of upgrading a diesel stock by using the Unisar process is shown in Table 8.6.2. The feedstock properties are shown in the first column. In this example, the feed is light cycle oil (LCO) from a fluid catalytic cracking unit (FCCU). The LCO has 69.9 wt % aromatics and a cetane number of less than 21. The second column shows the results of using the integrated Unionfining-Unisar process to reduce the aromatics content down to low levels. The aromatics have been reduced to 4 wt %, and the cetane number has increased to 44.4.

TABLE 8.6.1

Typical Applications Distillate 37.8 0.8358 501595 (261313) 3150 24.6 101.7 39.0 0.8299 2 1.0 760 Kerosene 41.3 0.8189 301567 (149297) 340 28.2 102.1 43.0 0.8072 Nil 3.0 745 Solvent stock 63.7 0.7249 208277 (98136) 2 10.0 101.7 65.8 0.7173 Nil 0.5 330

Feedstock type Feedstock properties: API gravity Specific gravity Boiling range, F (C) Sulfur, wt ppm Aromatics, vol % C5 + yields, vol % Product properties: API gravity Specific gravity Sulfur, wt ppm Total aromatics, vol % Hydrogen consumption, SCFB
Note: API

degrees on American Petroleum Institute scale.

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UOP UNISAR PROCESS FOR SATURATION OF AROMATICS 8.66 TABLE 8.6.2 Process
HYDROTREATING

LCO Upgrading with the Unionfining/ Unisar LCO Feed Product 0.852 (34.6) 0 0 11.7 84.4 3.9 0.1 0.0 0 0 44.4 45.3

API gravity Sulfur, wt % Nitrogen, ppm Hydrocarbon types: Paraffins Naphthenes Monoaromatics Diaromatics Triaromatics Heterocompounds Olefins Cetane number Cetane index, D-976

0.942 (18.7) 1.39 1107 6.6 6.1 26.7 36.1 7.1 14.8 2.5 21 26.6

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