The present invention relates to a process of alkylating an isoparaffin.

Alkylation is a reaction in which an alkyl group

5 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 to C ₅ olefin with isobutane in the presence of 0 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 5 have historically used hydrofluoric or sulfuric acid catalysts under relatively low temperature conditions. The sulfuric acid alkylation reaction is particularly sensitive to temperature, with low temperatures being favored to minimize the side 0 reaction of olefin polymerization. Acid strength in these liquid acid catalyzed alkylation processes is preferably maintained at 88 to 94 weight percent by the continuous addition of fresh acid and the continuous withdrawal of spent acid. The 5 hydrofluoric acid process is less temperature sensitive and the acid is easily recovered and purified.

Both sulfuric acid and hydrofluoric acid alkylation share inherent drawbacks including 0 environmental and safety concerns, acid consumption, and sludge disposal. Research efforts have been directed to developing alkylation catalysts which are equally as effective as sulfuric or hydrofluoric acids but which avoid many of the problems associated 5 with these two acids. 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. 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). With increasing demands for octane and increasing environmental concerns, it has been desirable to develop an alkylation process employing safer, more environmentally acceptable catalyst systems. Specifically, it is desirable to provide an industrially viable alternative to the currently used hydrofluoric and sulfuric acid alkylation processes. Consequently, substantial efforts have been made to develop a viable isoparaffin-olefin alkylation process which avoids the environmental and safety problems associated with sulfuric and hydrofluoric acid alkylation while retaining the alkylate quality and reliability characteristic of these well-known processes. Research efforts have been directed towards solid as well as liquid alkylation catalyst systems, as reflected in the following references.

U.S. Patent 3,862,258 teaches an alkylation process using a catalyst comprising a macroreticular acid cation exchange resin and boron trifluoride. According to the patent, the life of such a catalyst can be extended by the presence in the reaction mixture of closely controlled amounts of water which can be added to the feed as water or as water-forming compound. U.S. Patent 3,549,557 describes alkylation of isobutane with C -C_ olefins using certain crystalline alu inosilicate zeolite catalysts in a fixed-, moving- or fluidized bed system.

U.S. Patent 3,644,565 discloses alkylation of a paraffin with an olefin in the presence of a catalyst comprising a Group VIII noble metal present on a crystalline aluminosilicate zeolite. The catalyst is pretreated with hydrogen to promote selectivity.

U.S. Patent 3,647,916 describes an isoparaffin- olefin alkylation process featuring use of an ion- exchanged crystalline aluminosilicate, isoparaffin/olefin molar ratios below 3:1 and regeneration of the catalyst.

U.S. Patent 3,655,813 discloses a process for alkylating C -C ₅ isoparaffins with C_-C_ olefins using a crystalline aluminosilicate zeolite catalyst wherein a halide adjuvant is used in the alkylation reactor. The isoparaffin and olefin are introduced into the alkylation reactor at specified concentrations and catalyst is continuously regenerated outside the alkylation reactor.

U.S. Patent 3,917,738 describes a process for alkylating an isoparaffin with an olefin using a solid, particulate catalyst capable of absorbing the olefin. The isoparaffin and the olefin are admixed to form a reactant stream in contact with catalyst particles at the upstream end of an adsorption zone. Thereafter, the reactants are passed concurrently with the catalyst so that a controlled amount of olefin is adsorbed into the catalyst before the combination of reactants and catalyst is introduced into an alkylation zone. This controlled olefin adsorption is thought to prevent polymerization of the olefin during alkylation.

U.S. Patent 4,384,161 describes a process of alkylating isoparaffins with olefins to provide alkylate using a large-pore zeolite catalyst capable of absorbing 2,2,4-trimethylpentane, for example.

ZSM-4, ZSM-20, ZSM-3, ZSM-18, zeolite Beta, faujasite, mordenite, zeolite Y and the rare earth metal-containing forms thereof, and a Lewis acid such as boron trifluoride, antimony pentafluoride or aluminum trichloride. The use of a large-pore zeolite with a Lewis acid is reported to increase the activity and selectivity of the zeolite, thereby effecting alkylation with high olefin space velocity and low isoparaffin/olefin ratio. However, while it would be desirable to substitute a solid alkylation catalyst for the existing liquid catalysts, to date solid catalysts have not proven to be commercially viable alternatives due to problems with catalyst longevity and alkylate product quality. An object of the present invention is therefore to alleviate these problems.

The present invention includes a process for alkylating an olefin with an isoparaffin comprising contacting an olefin-containing feed with an isoparaffin-containing feed in the presence of a crystalline microporous material under alkylation conversion conditions including a temperature at least equal to the critical temperature of the principal component of the feed and a pressure at least equal to the critical pressure of the principal component of the feed.

In a preferred embodiment, the fresh crystalline microporous material contacts the mixed isoparaffin- olefin feed only under process conditions which are at least equal to the critical temperature and pressure of the principal component of the feed. Contacting the isoparaffin-olefin feed with the crystalline microporous material under supercritical

conditions and avoiding contact between the feed and the crystalline microporous material under subcritical conditions has been found to prolong the useful catalytic life of the crystalline microporous material.

Feedstocks useful in the present alkylation process include at least one isoparaffin and at least one olefin. The isoparaffin reactant used in the present alkylation process typically has 4 to 8 carbon atoms. Representative examples of such isoparaffins include isobutane, isopentane, 3- methylhexane, 2-methylhexane, 2,3-dimethylbutane and 2,4-dimethylhexane.

The olefin component of the feedstock typically has 2 to 12 carbon atoms. Representative examples of such olefins include butene-2, isobutylene, butene-1, propylene, ethylene, hexene, octene, and heptene. The preferred olefins include the C. olefins, for example, butene-1, butene-2, isobutylene, or a mixture of one or more of these C 4. olefins, with butene-2 being the most preferred. Suitable feedstocks for the process of the present invention are described in U.S. Patent 3,862,258 to Huang et al. at column 3, lines 44-56. Isoparaffin:olefin ratios in the reactor feed preferably range from 1.5:1 to 100:1 to produce a high-octane isobutane:butene alkylate product at industrially useful yields. Higher isoparaffin: olefin ratios may also be used, but limited availability of produced isoparaffin within the refinery coupled with the relatively high cost of purchased isoparaffin favor isoparaffin:olefin ratios within the ranges listed above.

The present alkylation process is suitably conducted at a temperature of 135 to 370 ^β C (275 to 700 ^β F), preferably 150 to 315 ^β C (300 to 600 ^β F) . Operating temperature must exceed the critical temperature of the principal component in the feed. The term "principal component" as used herein is defined as the component of highest concentration in the feedstock. For example, isobutane is the principal component in a feedstock consisting of isobutane and 2-butene in isobutane:2-butene weight ratio of 50:1.

Operating pressure is similarly controlled to maintain the principal component of the feed in the supercritical state, and is suitably from 2170 to 10400 Kpa (300 to 1500 psig) , preferably from 2860 to 7000 kPa (400 to 1000 psig) . Critical constants for various C4 hydrocarbons are shown below: Hydrocarbon Critical Constants

Temperature Pressure °F ( ^β C) psia (kPa) i-Butane 275.0 (135) 529.1 (3749) n-Butane 305.6 (152) 550.7 (3898)

1-Butene 295.6 (146.4) 583.0 (4121) cis-2-Butene 324.3 (162.4) 600.0 (4238) trans-2-Butene 311.9 (155.5) 600.0 (4238) i-Butylene 292.5 (144.7) 579.8 (4099)

In a preferred embodiment, the operating temperature and pressure remain above the critical value for the principal feed component during the entire process run, including the first contact between fresh catalyst and fresh feed.

Hydrocarbon flow through the alkylation zone containing the catalyst is typically controlled to

Crystalline microporous catalysts useful in the present invention include zeolites and layered materials. Zeolite catalysts which are useful in the alkylation process of this invention include those possessing a Constraint Index of not greater than about 12. The method by which Constraint Index is determined is described fully in U.S. Patent No. 4,016,218. Constraint Index (CI) values for some typical zeolites including some which are suitable as catalysts in the process of this invention are: CI at test tem erature.

Some zeolite catalysts which are particularly useful in the process of this invention include zeolites ZSM-4, ZSM-12, ZSM-20, ZSM-35, ZSM-48, ZSM- 50, MCM-22, MCM-49, PSH-3, TMA offretite, TEA mordenite, clinoptilolite, mordenite, REY and zeolite Beta. Of these, zeolites ZSM-12, MCM-22, MCM-49 and Beta are preferred.

Zeolite ZSM-4 is taught in British Patent No. 1,117,568; ZSM-12 in U.S. Patent No. 3,832,449; ZSM- 20 in U.S. Patent No. 3,972,983; ZSM-35 in U.S. Patent No. 4,016,245; ZSM-48 in U.S. Patent No. 4,397,827; ZSM-50 in U.S. Patent No. 4,640,849; MCM-22 in U.S. Patent 4,954,325; MCM-49 in International Publication No. WO 92/22498; zeolite Beta in U.S. Patent No. 3,308,069, and PSH-3 in U.S. Patent 4,439,409.

The zeolite selected for use in the present alkylation process generally exhibits an alpha value over a wide range of from less than 1 to more than 1000. The index "Alpha value" measures zeolite acidic functionality and is described in detail in 61 J. Catalysis 395 (1980).

Additional molecular sieves which find utility in conjunction with the present invention include pillared silicates and/or clays; aluminophosphates, e.g. ALPO-5, VPI-5; silicoaluminophosphates, e.g. SAPO-5, SAPO-37, SAPO-31, SAPO-40, SAPO-41; and other metal aluminophosphates. These are variously described in U.S. Patents 4,440,871; 4,554,143; 4,567,029; 4,666,875; and 4,742,033.

The pillared layered material MCM-36, which is described in International Publication No. 92/11934, is also a useful catalyst in the process of the invention.

The microporous crystalline catalyst employed in the present invention may be combined with an inorganic oxide binder, such as alumina, silica, boria, oxides of phosphorus, titanium dioxide, zirconium dioxide, chromia, zinc oxide, magnesia, calcium oxide, silica-alumina, silica-magnesia, silica-alumina-magnesia, silica-alumina-zirconia, as well as the naturally occurring inorganic oxides of various states of purity such as bauxite, clay, and diatomaceous earth. The preferred inorganic oxide binders are amorphous silicon dioxide and aluminum oxide.

The invention will now be more particularly described with reference to the Examples and the accompanying drawing, which is a graph plotting weight percent olefin conversion as a function of days on stream for isobutane/2-butene alkylation in the presence of an MCM-22/A1-0- extrudate catalyst.

EXAMPLES 1 - 9 Examples 1-9 show isoparaffin-olefin alkylation over different synthetic crystalline materials. These experiments evaluate the effects of altering reaction zone temperature and pressure, on the alkylation activity, selectivity, and longevity of various synthetic crystalline materials. While several materials appeared promising under start-of- run conditions, their alkylation performance generally deteriorated with increasing time on stream. For a crystalline material to be a viable candidate for commercialization, it must retain a useful level of catalytic activity over time, preferably to maximize time on stream between regenerations or catalyst replacements. The following examples surprisingly show that controlling temperature and pressure to maintain the principal

component of the feed in the supercritical state not only improves start-of-run performance, but also prolongs the useful life of the solid catalyst (i.e., the synthetic crystalline material) . Experimental Procedure

The following experiments were performed in a fixed-bed reactor. Typically, 5 grams of catalyst (30/60 mesh) was loaded into a fixed-bed reactor and the catalyst was heated overnight in a stream of nitrogen at the operating temperature and pressure. A pre-mixed hydrocarbon feed (obtained from Matheson and used as received) was introduced to initiate the run.

The hydrocarbon product, after depressurizing, was passed through a glass condenser. The condensed liquid and off-gas were analyzed separately by gas chromatography to determine conversion and selectivity.

Examples 1-3 in Table 1 show the effect of temperature on the activity and selectivity of MCM- 36/Al_0_ catalyst. In each example the reactor pressure is 4240 kPa (600 psig) and is above the critical pressure of isobutane, the principal feed component. In examples 1 and 2, where the reactor temperature is at or above the critical temperature of isobutane, the olefin conversion is maintained at >99 wt%. However, in example 3, where the reactor temperature is below the critical temperature of i- butane, the olefin conversion decreases significantly to 86.3%.

Examples 4-9 in Table 2 show the effect of pressure on the activity and selectivity of MCM- 22/Al ₂ 0 ₃ , MCM-49/Al ₂ 0 ₃ , and MCM-36/Al ₂ 0 ₃ catalysts. In each example the reactor temperature is 149 ^β C (300 ^β F) and is above the critical temperature of isobutane, the principal feed component. With each catalyst high olefin conversion is obtained at 4930 kPa (700 psig) which is above the critical pressure of i-butane. However, with each catalyst the olefin conversion is significantly reduced when the reactor pressure is reduced to 3548 kPa (500 psig) which is below the critical pressure of isobutane.

TABLE 2

Alkylation with Zeolite/Al.O Catalysts Comparison of Subcritical versus supercriti

Pressure Conditions

Catalyst MCM-22/Al ₂ 0 ₃ MCM-49/Al ₂ 0 ₃ MCM-36/Al ₂ 0 ₃

Extrudate Extrudate Extrudate

Example No. 4 5 8

Reaction Conditions:

Feed I/O 50

Pressure psig 500 7

(kPa) 3548 49

Time on Stream

(days) 1.5

C ₄ = WHSV (hr ^-1 ) 0.05 Conv. (wt%) 46.7

C ₅ + yield (gram/gram

CC..== CCoonnvv..)) 1.6 1.8 1.6 1.9 1.6 1.9

C-+ Analysis: Total C \'8, 73 63 60 58 56 53

^C 9 ⁺ 17 15 14 15 18 14 Unknown C_ 19 5. 5.2 2.0 4.4 1.1

TMP/DMH 2.3 2. 3.2 3.0 2.1 2.3

TMP/(DMH+Unk. C ) 1.1 2. 2.3 2.6 1.6 2.2

Examples 1-9 show the improvement in isoparaffin-olefin alkylation activity resulting from maintaining reaction conditions above the critical values for the principal component of the feed. The alkylation process of the invention is preferably started and maintained under supercritical condition, as shown in the drawing which shows the improvement in catalyst stability when the startup is carried out at 4930 kPa (700 psig) and 149°C (300°F) . The circular datapoints in the drawing represent data from a run where the startup is carried out at 3548 kPa (500 psig) and 149°C (300°F) . Starting at 100%,

the olefin conversion decreased rapidly to less than about 50% within 2.5 days on stream. Increasing the pressure to 4930 kPa (700 psig) improved the conversion but the conversion remained below 80%. On the other hand, starting and maintaining the run under supercritical conditions provided olefin conversion of greater than about 95% for more than 6 days on stream, as shown by the triangular datapoints in the drawing.