The present invention relates to an isoparaffin-olefin alkylation process.

Alkylation is a reaction in which an alkyl group is added to an organic molecule. Thus an isoparaffin can be reacted with an olefin to provide an isoparaffin of higher molecular weight. Industrially, the concept depends on the reaction of a C ₂ to C ₅ olefin with isobutane in the presence of an acidic catalyst producing a so-called alkylate. This alkylate is a valuable blending component in the manufacture of gasolines due not only to its high octane rating but also to its sensitivity to octane-enhancing additives.

Industrial alkylation processes have historically used concentrated hydrofluoric or sulfuric acid catalysts under relatively low temperature conditions. Acid strength is preferably maintained at 88 to 94 weight percent by the continuous addition of fresh acid and the continuous withdrawal of spent acid. As used herein, the term "concentrated hydrofluoric acid" refers to an essentially anhydrous liquid containing at least about 85 weight percent HF.

Hydrofluoric and sulfuric acid alkylation processes share inherent drawbacks including environmental and safety concerns, acid consumption, and sludge disposal. For a general discussion of sulfuric acid alkylation, see the series of three articles by L.F. Albright et al., "Alkylation of Isobutane with C ₄ Olefins", 27 Ind. Eng. Chem. Res. , 381-397, (1988). For a survey of hydrofluoric acid catalyzed alkylation, see 1 Handbook of Petroleum Refining Processes 23-28 (R.A. Meyers, ed. , 1986).

Hydrogen fluoride, or hydrofluoric acid, (HF) is highly toxic and coorsive. However, years of experience in its manufacture and use have shown that HF can be handled safely, provided the hazards are recognized and precautions taken. Though many safety precautions are taken to prevent leaks, massive or catastrophic leaks are feared primarily

because the anhydrous acid will fume on escape creating a vapor cloud that can be spread for some distance.

Previous workers in this field have approached this problem from the standpoint of containing or neutralizing the HF cloud after its release. Thus U.S. Patents 4,938,935 and 4,985,220 to Audeh and Greco, as well as U.S. Patent 4,938,936 to Yan teach various methods for containing and/or neutralizing HF acid clouds following accidental releases. In addition, it has been proposed to provide an additive which decreases the cloud forming tendency of HF without compromising its activity as an isoparaffin- olefin alkylation catalyst. For example, O93/00314 discloses a method for increasing rainout from an autorefridgerated vaporous cloud containing HF by admixing the HF with a sulfone component, preferably sulfolane. Isoparaffin-olefin alkylation processes typically convert at least a portion of the feedstock to conjunct polymeric byproducts, which are more commonly referred to as acid soluble oil or ASO. Adding sulfolane to HF for isoparaffin-olefin alkylation complicates the problem of removing ASO from the system because the typical boiling range of the ASO brackets the boiling point of sulfolane (285°C, 545°F). Thus sulfolane cannot be readily separated from ASO by distillation. U.S. Patent 5,191,150 teaches a sulfolane recovery method which involves reducing the HF concentration in a mixture of HF, sulfolane, and ASO to less than about 30 weight percent and then gravitationally separating the resulting for a mixture to recover sulfolane. The sulfolane-enriched stream recovered from this gravitational separation step typically contains less than about 10 weight percent water, and is preferably dried to a water content of 2 to 8 weight percent water for optimum alkylation performance. Drying the sulfolane stream has, in the past, required stripping the sulfolane with an inert stripping fluid such as isoparaffin (i.e. isobutane) or

nitrogen. It would be desirable to simplify and still further improve the process of U.S. Patent 5,191,150 by eliminating the sulfolane drying step.

In accordance with the invention, it has been discovered that drawing a side stream from the catalyst stripper tower eliminates the need for drying the sulfolane fraction which is produced from the downstream gravitational separation step. The stripped mixture containing sulfolane, ASO, and HF then separates (in the downstream gravitational separation step) into (a) a less dense stream containing alkylate, isobutane, and a first ASO fraction; and (b) a more dense stream containing sulfolane (which requires no further drying before recycling the sulfolane to the alkylation reaction zone) and a second ASO fraction.

Accordingly, the present invention resides in an isoparaffin-olefin alkylation process comprising the sequential steps of:

(a) alkylating an isoparaffin with an olefin in the presence of an alkylation catalyst comprising HF and sulfolane in an alkylation reaction zone to produce alkylation product and acid soluble oil (ASO) byproduct;

(b) gravitationally separating effluent from said alkylation reaction zone to provide a less-dense stream containing alkylate product and unreacted isoparaffin and a more dense stream containing sulfolane, ASO, and HF;

(c) stripping HF from said more dense stream of step (b) with isoparaffin in a multistage stripper column to provide a stripper bottoms stream containing less than about 30 percent HF by weight, a stripper overhead stream containing HF, isoparaffin and a fraction of said ASO having a lower end boiling point than the ASO containing in said more dense stream of step (b) , and a water-enriched side stream; and

(d) gravitationally separating said stripper bottoms stream into a more dense sulfolane-enriched stream and a less dense ASO-enriched stream.

In the process of the invention, the HF concentration of the mixture is preferably decreased by stripping. Any suitable inert stripping fluid may be employed, including normal paraffins and isoparaffins which can be charged to the stripper tower as a vapor. Isobutane and the vaporized alkylate product formed by reacting isobutane with butene are particularly preferred stripping fluids. Two sequential stripping steps may be used, as the purity of the separated sulfolane/ASO phases improves as the HF concentration decreases. If two-stage stripping is used, the enriched stripping fluid from both stripping stages is preferably charged to the product fractionator.

The effects of sequentially stripping HF from the mixture before gravitational separation become particularly evident as the mixture is stripped to HF levels of less than about 30 weight percent. Separation improves as the HF content is decreased, with intermediate stream HF concentrations preferably falling below 25 percent by weight, more preferably below about 10 percent HF by weight, and most preferably below about 5 percent by weight. In a preferred embodiment, the catalyst mixture contains from 0.5 to 10 weight percent water.

During continuous operation, the HF/sulfolane alkylation catalyst can accumulate or lose water. Making up lost water is relatively straightforward, and water can be injected into the process at essentially any point, preferably upstream of the alkylation reactor.

The invention will now be more particularly described with reference to the accompanying drawings, in which:

Figure 1 is a simplified schematic diagram showing the major processing steps in the method of the invention.

Figure 2A shows the infrared (IR) spectrum of the ASO from the lower-density phase withdrawn from the gravitation separation step of the invention.

Figure 2B shows the IR spectrum of the higher density phase withdrawn ^• from the gravitational separation step of the invention.

Figure 2C shows the IR spectrum of sulfolane extracted from the higher density phase withdrawn from the gravitational step of the invention. Figure 3 shows a simulated distillation comparing the boiling ranges of components in the conjunct polymeric byproducts (referred to herein as acid soluble oil or ASO) from the lower density phase of the gravitational separation step with the ASO from the higher density phase of the gravitational separation step of the invention. Referring now to Figure 1, mixed isoparaffin and olefin feed 10 and liquid catalyst 12 flow to riser/reactor 20. The riser/reactor effluent 22 flows to gravitational separator 30 where the effluent separates into a less dense hydrocarbon stream 38 containing alkylate and unreacted isoparaffin and a more dense catalyst stream 32 which contains HF, sulfolane, and ASO. The majority of the catalyst stream 32 recycles to riser/reactor 20 via stream 36, optionally through catalyst recycle pump 40, and stream 16. Fresh makeup HF enters stream 16 as required via stream 14. A minor amount of catalyst stream 32 flows to catalyst stripper 50 via stream 34. Isoparaffin (typically isobutane) from stream 52 strips HF and a lighter boiling fraction of the ASO from the catalyst mixture to produce a stripped catalyst stream 54 containing less than about 30 weight percent HF. The stripping fluid (isobutane) , now enriched in HF and a lighter boiling fraction of the ASO, flows to product fractionator 90 as stream 56.

Vapor side draw 58, principally containing isobutane and water, condenses in side draw cooler 100 and flows as a total condensate 102 to side draw accumulator 110. The

total condensate separates within side draw accumulator 110 into a less-dense hydrocarbon phase and a more-dense aqueous phase. The less-dense hydrocarbon phase, which is enriched in isobutane, is withdrawn from the side draw accumulator 110 through line 112, and the more-dense aqueous phase is withdrawn through line 114. The hydrocarbon phase may then be optionally recycled to alkylation reactor 20.

The stripped catalyst, stream 54, flows to cooler 60 from the catalyst stripper at tower temperature of about 150°C (300°F), and is cooled to about 20°C (70°F) . The cooled stripped catalyst stream 68 enters gravitational separator 70 at approximately atmospheric pressure.

Two liquid phases form within gravitational separator 70. The upper, less dense phase, enriched in ASO, collects near the top 72 of gravitational separator 70, and is withdrawn through line 76 for further processing, as described below. Solids and the most dense residual hydrocarbons collect in a bottom boot 74, and are similarly withdrawn for further processing as stream 78. The lower, more dense liquid phase, enriched in sulfolane, flows out of gravitational separator 70 as stream 77, and may be recycled directly to alkylation riser/reactor 20, or may optionally be further purified, e.g., by vacuum distillation. Figure 1 illustrates an embodiment showing the optional vacuum distillation steps. Referring again to Figure 1, stream 77 enters a lower middle section of vacuum distillation column 80, which operates at a feed tray temperature of about 150°C (300°F) and the maximum available vacuum. The sulfolane and ASO readily separate in vacuum distillation column 80, with the sulfolane flowing overhead as stream 82 and the ASO leaving the column as stream 84. The sulfolane overhead stream 82 may then be partially or totally recycled to alkylation riser/reactor 20 with no intermediate drying step.

Streams 38 and 56 flow to product fractionator 90,

with stream 56, the isobutane stripping fluid enriched in HF and a lighter boiling fraction of the ASO, preferably entering product fractionator 90 on a tray above the feed tray for stream 38. The overhead stream 92 from product fractionator 90, enriched in isobutane and HF, condenses in overhead cooler 94 and separates into a hydrocarbon phase and an acid phase in overhead accumulator 120. The hydrocarbon phase, enriched in isobutane, leaves accumulator 120 as stream 122, and splits between reflux stream 123 and isobutane recycle stream 125. The acid phase in accumulator 120 settles in the lower boot section 130 of the accumulator and is withdrawn as stream 124 for recycle to riser/reactor 20. Alkylate product, containing a minor amount of light ASO, flows from product fractionator 90 as stream 96, while n-butane is withdrawn as side draw 98. Comparative Example

A mixture of HF, sulfolane, and ASO byproducts (which are polymeric byproducts evolved from the catalytic alkylation of isobutane with butene) containing about 65 weight percent HF, 30 weight percent sulfolane and about 5 weight percent ASO, is charged to a decantation vessel at ambient temperature and pressure sufficient to maintain the mixture in the liquid phase. The mixture is allowed to stand for approximately 24 hours. No phase separation is observed.

Example 1 A mixture of HF, sulfolane, and ASO (having the same composition as the mixture of the Comparative Example, above) is charged to a stripping tower having three theoretical stages. Isobutane is introduced into the tower at a level below the height of the liquid (HF/sulfolane/ASO) charge point, and the isobutane and mixture charge rates are controlled to maximize stripping of HF while operating below the flooding point of the

tower. A stripped liquid is withdrawn from the bottom of the tower and a HF-enriched isobutane stream is withdrawn from the top of the tower. The stripped liquid contains less than about 30 percent by weight of hydrofluoric acid.

The stripped liquid is then charged to a decantation vessel and allowed to stand for approximately 24 hours. The mixture separates into two distinct phases, an upper, less dense ASO-enriched phase, and a lower, more dense, sulfolane-enriched phase.

Examples 2-4

Additional samples of the mixture of HF, sulfolane, and ASO (having the same composition as the mixture of the Comparative Example) are stripped with isobutane to HF contents of 25 weight percent, 10 weight percent, and 5 weight percent, respectively. The stripped mixtures containing lower concentrations of HF separate more readily than mixtures having higher HF concentrations.

Example 5

The HF/sulfolane sample of Example 5 has the following composition:

Component Weight Percent

HF 62

Sulfolane 27

Isobutane 4

Water 1-2

ASO 3

Balance - Other to 100% Hydrocarbons

This mixture is a single liquid phase at 32 "C (90°F) and 930 kPa (120 psig) .

The sample is brought to atmospheric pressure and room temperature and most of the light hydrocarbons and part of

the HF are vented off. Under these conditions, the sample is a single liquid phase containing about 50 wt. % HF.

Nitrogen is then bubbled through the mixture at room temperature and atmospheric pressure to strip HF off the mixture. As the mixture is depleted in HF, the mixture separates into two phases.

Both phases are analyzed, and the dense phase (specific gravity about 1.26) contains 83.2 wt. % sulfolane, 2.2 wt. % ASO, and the balance water, salts, and a sludge. The lighter phase, having a density of less than about 1, contains 82.8 wt. % ASO, 13.3 wt. % sulfolane, and the balance of salts.

Figure 2 shows the IR spectra of ASO from the lighter phase (the upper spectrum) , ASO from the heavier phase (the middle spectrum) and sulfolane (the lower spectrum) . Figure 3 shows simulated distillations of ASO fractions from the low density phase and the high density phase from the gravitational separation step. The initial boiling point and the endpoint for the low density phase are both different from the corresponding points for the high density phase. Thus the gravitational separation splits the ASO into two fractions having different, albeit overlapping, boiling ranges.

Example 6 The sulfolane-enriched dense phase of Example 5 is charged to a vacuum distillation column under the maximum available vacuum. The column bottom temperature is about 150°C (300°F) . The overhead stream withdrawn from the distillation column is highly enriched in sulfolane while the bottoms product predominantly contains the higher boiling ASO fraction contained in the more-dense phase of Example 5.

Example 7 A catalyst mixture containing about 65 wt.% HF, 30 wt.% sulfolane, and about 5 wt.% ASO is fed to a catalyst stripper column at a rate of about 320 m ³ /ά.ay (2,000

barrels per day, BPD) . The catalyst stripper column operates at about 1100 kPa (150 psi) . Isobutane (as stripping fluid) is charged to the catalyst stripper tower at a rate of about 15890 kg/hr (35,000 lb/hr) to strip HF and a light fraction of the ASO from the catalyst mixture. The bottom stream from the catalyst stripper tower contains approximately 82 wt.% sulfolane and the balance HF, heavy ASO, and hydrocarbons. From the top of the catalyst stripper column, about 15890 kg/hr (35,000 lb/hr) of isobutane, 7718 kg/hr (17,000 lb/hr) of HF, and 363 kg/hr

(800 lb/hr) of ASO at about 90°C (200°F) are sent to the an upper (stripping) section of a main product fractionator. The principal feeds to the main product fractionator are about 431300 kg/hr (950,000 lb/hr) of hydrocarbon alkylation reactor effluent, which predominately comprises isobutane with about 15 wt.% alkylate. The overhead stream from the main product fractionator, about 340500 kg (750,000 lb.) of hydrocarbon and HF, is condensed and separated into two phases: an isobutane-rich phase saturated in HF and essentially free of ASO, and an HF phase, saturated in isobutane and essentially free of ASO.

A small side stream removes n-butane from the main product fractionator. The bottoms product, mainly alkylate and ASO, is sent to an alkylate product storage tank. Of the total charge to the product fractionator, the acid-rich feed from the top of the catalyst stripper column typically accounts for about 3.5 to about 4%, and the light ASO fraction typically comprises about 0.7 wt.% of the alkylate product stream withdrawn from the product fractionator. Example 8

Referring now to Figure 1, Example 8 illustrates an embodiment of the invention showing typical flowrates and stream compositions for the process streams surrounding catalyst stripper 50, side draw cooler 100, and side draw liquid accumulator 110. For the purposes of Example 8, catalyst stripper 50 is assumed to contain five tray stages

with stream 34 entering the stripper column at a point above the uppermost tray. Side draw stream 58 is withdrawn as a vapor at a point above the fourth stage (counting stages from the top of the column) . The isobutane stripping fluid 52 enters the catalyst stripper 50 at a point below the fifth stage (counting from the top of the column) .

Example 8 Stream Compositions

Stream Number 34 52 54 56 58/102 112 114

Component, wt. %

Isobutane 0.0 100.0 0 56.3 86.8 95.0 0

HF 66.2 0 2.0 42.5 6.89 0.8 52.5

ASO 3.2 0 9.7 0 0.06 0 0

Sulfolane 28.42 0 87.9 0 0.3 0 2.4

Water 2.1 0 0.4 1.2 5.93 0.01 45.1

Total 6500 31200 «115 «98 14.9

Flowrate, lb/hr (kg/hr) (2950) (14165) («52) («44) (6.8)

The less-dense hydrocarbon stream 112 withdrawn from side draw accumulator 110 may be recycled as feed to the alkylation reactor 20, while the HF-enriched aqueous stream 114 may be partially recycled to alkylation reactor 20 or neutralized for disposal.